Dalian Institute Of Chemical Physics Research Articles

A Time of Change

Fresh faces: Read Editor-in-Chief Claire M. Cobley's editorial to find out more about our new board members, the 2023 Ryoji Noyori ACES Award winner, and new ACES early career awards. The beginning of a new year is always a time of change, and this year even more so than most at ChemNanoMat. After eight years of service, two founding co-chairs of the Editorial Board, Susumu Kitagawa, Kyoto University, Japan, and Huisheng Peng, Fudan University, China, will be stepping down from their roles this year. They have given excellent guidance to the journal from before the first papers were even published and were central to the journal's successful launch in 2015. We would like to express our heartfelt appreciation to them both for their numerous contributions! Thankfully they are not going far, and will continue to stay connected to the journal through roles on the International Advisory Board. This year we also say goodbye to many of our other founding board members. Their connections to the scientific community have been crucial in putting ChemNanoMat on the map and helping us turn the idea of a nanoscience journal rooted in Asia into a reality. The team would like to say a big thank you to all of them for everything they have done for the journal over the years. Although we are sad to say goodbye to old friends, we are also excited to announce that many fresh faces are joining ChemNanoMat’s editorial and advisory boards in 2023. Pooi See Lee, Nanyang Technological University, Singapore, will be joining Hua Zhang, City University of Hong Kong, as a co-chair of the Editorial Board starting this year. She was among the first authors to publish in ChemNanoMat after the journal's 2015 launch, and we are delighted to have her bring her deep expertise in nanomaterials for energy and electronics applications to the co-chair role. You can find the biographies of Pooi See Lee and the rest of our new Editorial Board members at the end of this editorial. We look forward to working with all of them to further grow and develop ChemNanoMat in the years to come. I would also like to take a moment to share two important pieces of news from the Asian Chemical Editorial Society (ACES), the collaboration of 12 chemical societies across Asia and the Pacific that co-own ChemNanoMat. First of all, we are delighted to announce that Keiji Maruoka, Kyoto University, Japan, will be the recipient of the 2023 Ryoji Noyori ACES Award. This award is given every two years to a field-leading chemist in honor of Ryoji Noyori's key role in the founding of ACES and launch of the first ACES journal, Chemistry – An Asian Journal. We are currently planning an award symposium to celebrate Professor Maruoka's award at the IUPAC-CHAINS meeting in The Hague, The Netherlands, in August of this year. We hope you will join us there! Second, ACES has recently launched a new award series designed to highlight the achievements of early career scientists. These awards are given by individual society partners on behalf of ACES and include both an invitation to speak at a national meeting and an invitation to submit an article to one of the three ACES journals: Chemistry – An Asian Journal, the Asian Journal of Organic Chemistry, and ChemNanoMat. We look forward to publishing the work of many award winners in the future! It has been a pleasure to work with all of you over the past year. Here's to another great year and many more fruitful collaborations! Dr. Claire M. Cobley Editor-in-Chief ChemNanoMat Pooi See Lee received her Ph.D. degree from the National University of Singapore in 2002. She joined Chartered Semiconductor Manufacturing Ltd (now Globalfoundries) in the research and technology development department from 2002–2003. She is a recipient of the 2001 Norman Hackerman Young Author award presented by the Electrochemical Society, USA. In January 2004, she joined the School of Materials Science and Engineering, Nanyang Technological University as an Assistant Professor. She was promoted to tenured Associate Professor in 2009. In Sept 2015, she was promoted to Full Professor. Pooi See has authored and co-authored many publications in the field of nanomaterials for energy and electronics applications. She is interested in synthesizing innovative nanomaterials and harnessing their multi-functionality through understanding the structure-property characteristics. She has developed high energy capacitors, energy saving electrochromic coatings, novel transparent conductors, flexible and stretchable devices. She is keen on advancing the frontier of green nanotechnology and to translate research outcomes into real solutions. She was elected as the National Academy of Inventors (NAI) Fellow in 2020, the highest professional distinction accorded solely to academic inventors. Rona Chandrawati is a Scientia Associate Professor and NHMRC Emerging Leadership Fellow in the School of Chemical Engineering at The University of New South Wales (UNSW Sydney), Australia. She obtained her Ph.D. from The University of Melbourne in 2012 and was then a Marie Curie Fellow at Imperial College London before returning to Australia as a Lecturer (2015–2017), Scientia Senior Lecturer (2018–2020), and Scientia Associate Professor (2021-present). Her research group focuses on developing enzyme-like catalysts for drug delivery and designing polymer-based nanomaterials for sensors in food safety and health monitoring. Hyunjoo Lee received her B.S. and M.S. degree from Seoul National University, South Korea and Ph.D. degree from California Institute of Technology, USA. She is currently a full professor at KAIST. Her research interests include heterogeneous atomic catalysts with structure control and their applications for various gas-phase and electrochemical reactions. Yan Lu received her Ph.D. in macromolecular chemistry in 2005 at the Dresden University of Technology, Germany. After that, she worked first as postdoctoral researcher and then as a research scientist at the University of Bayreuth. In 2009, she joined the Helmholtz-Zentrum Berlin für Materialien und Energie (HZB) as a group leader in Colloid Chemistry. Since 2017, she is a professor in the Institute of Chemistry at the University of Potsdam. She is now the head of the Department for Electrochemical Energy Storage at HZB. Her research focuses on design and synthesis of colloidal particles with tailored mesoscopic structures and their application as energy storage materials, catalysts and sensors. Pramod Pillai obtained his B.Sc. and M.Sc. from Mahatma Gandhi University in Kerala, India, followed by a Ph.D. in Chemistry from Cochin University of Science & Technology, in Kerala, India (work done at National Institute for Interdisciplinary Science and Technology (NIIST), Trivandrum, India). His Ph.D. research was on the optical properties of hybrid nanomaterials, in the group of Prof. K. George Thomas. After graduation, he worked as an Alexander von Humboldt postdoctoral fellow at Technische Universität Dortmund, Germany, in the group of Prof. Christof M. Niemeyer. This was followed by a second postdoctoral stay at Northwestern University in Evanston, U.S.A., in the group of Prof. Bartosz A. Grzybowski. During his postdoctoral research, he worked on interdisciplinary areas in nanoscience including nanoelectronics and nanobiotechnology. Currently, he is an Associate Professor in the Department of Chemistry at the Indian Institute of Science Education and Research (IISER) Pune, India. His research at IISER Pune is focused on the interplay of forces to control the light-matter interactions at the nanoscale. Some of the properties of interest include (photo)catalysis, trivial & non-trivial photophysics, and self-assembly in hybrid nanomaterials. Bing Xu, after receiving his B.S. and M.S. degrees from Nanjing University in 1987 and 1990, respectively, obtained his Ph.D. in 1996 from the University of Pennsylvania. Before starting his independent research at the Hong Kong University of Science and Technology (HKUST) in 2000, he was an NIH postdoctoral fellow at Harvard University. Dr. Xu was a tenured professor at HKUST until Jul. 2008 before he returned to Boston. He currently is a professor in the Department of Chemistry, Brandeis University. He has made pioneering contributions to metallogels, multifunctional magnetic nanoparticles, self-delivery drugs, supramolecular hydrogels, and enzyme-instructed self-assembly for in-situ anticancer nanomedicine. His current research focuses on the applications of enzymatic noncovalent synthesis in materials, biology, and medicine. Nobuhiro Yanai is an Associate Professor in the Department of Applied Chemistry at Kyushu University, Japan. He earned his Ph.D. from Kyoto University in 2011 under Prof. Susumu Kitagawa and Prof. Takashi Uemura on guest properties in metal-organic frameworks (MOFs)/porous coordination polymers (PCPs). He was a postdoctoral fellow with Prof. Steve Granick at the University of Illinois at Urbana-Champaign, experiencing colloid and soft matter sciences. He joined Kyushu University in 2012. He is currently leading a group that creates photo-functional materials, working on photon upconversion, dynamic nuclear polarization, and quantum materials. He received several awards including The Wiley Young Researcher Award, The APA (Asian and Oceanian Photochemistry Association) Prize for Young Scientists, and Award for Young Chemists, Chemical Society of Japan (CSJ). Qihua Yang received her Ph.D. degree in Inorganic Chemistry from Northeast Normal University. She did postdoctoral research in State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics (DICP, China), LCOMS-CNRS/CPE (France), and Toyota Central R&D Labs. Inc. (Japan). She joint DICP as a full professor in 2003 and moved to Zhejiang Normal University in 2022. Her research interests are mainly focused on the synthesis of hybrid porous materials for heterogeneous asymmetric catalysis and nano-catalysis. She is the author or co-author of more than 200 peer-reviewed scientific publications.

Copper-Catalyzed Ligand-Controlled Selective Borocarbonylation of α-Substituted Styrenes Toward β-Boryl Aldehydes and Cyclopropyl Boronate Esters

Open AccessCCS ChemistryRESEARCH ARTICLES18 Oct 2022Copper-Catalyzed Ligand-Controlled Selective Borocarbonylation of α-Substituted Styrenes Toward β-Boryl Aldehydes and Cyclopropyl Boronate Esters Yang Yuan†, Youcan Zhang†, Jian-Xing Xu and Xiao-Feng Wu Yang Yuan† Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023 Liaoning †Y. Yuan and Y. Zhang contributed equally to this work.Google Scholar More articles by this author , Youcan Zhang† Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023 Liaoning †Y. Yuan and Y. Zhang contributed equally to this work.Google Scholar More articles by this author , Jian-Xing Xu Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023 Liaoning Google Scholar More articles by this author and Xiao-Feng Wu *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023 Liaoning Leibniz-Institut für Katalyse e.V., Albert-Einstein-Straße 29a, Rostock 18059 Google Scholar More articles by this author https://doi.org/10.31635/ccschem.022.202202288 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail We report a copper-catalyzed ligand-controlled selective carbonylative borofunctionalization of α-substituted styrenes. This reaction provides a general and versatile procedure to synthesize a variety of synthetically useful β-boryl quaternary aldehydes and cyclopropyl boronate esters bearing a quaternary carbon center. With NHC (IMes= 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) as the ligand, the carbene intermediate reacts with O–H bond of alcohol while the carbene intermediate would undergo C–H bond insertion when using phosphine ligand [1,2-bis(diphenylphospino)ethane] as the ligand. Formation of a carbene intermediate has been proposed as the key step for this transformation. Download figure Download PowerPoint Introduction Carbenes or carbenoids are important reactive intermediates in organic synthesis that allow for the rapid construction of highly functionalized molecules.1–7 Among them, due to their electrophilic property, Fischer-type carbene and free carbene species can undergo insertion reactions.8,9 These insertion reactions, especially transition-metal-catalyzed carbene insertion reactions, represent one of the most fundamental and synthetically useful methods for forging C–C bonds or C–X bonds with high selectivity. Therefore, great effort has been devoted to the development of carbene insertions into C–H, N–H, O–H, S–H, and other X–H (e.g., B–H, Si–H, P–H…) bonds in past decades (Scheme 1a).10–23 Despite tremendous progress in this field, the selectively controlled X–H insertion under similar catalytic systems that allows for the structural diversity of final products, is still needed but remains challenging in current synthetic chemistry. Scheme 1 | Carbene insertion into X–H bond reactions. Download figure Download PowerPoint In recent years, borofunctionalization of unsaturated bonds has emerged as a remarkably versatile method to install boron (or boron and other functionalities) across π-systems.24–32 Among the possible procedures, transition-metal-catalyzed borocarbonylation33–39 is one of the most direct and efficient methods, introducing both the carbonyl group and the boryl group into a single molecule in one pot. Several approaches have been studied in our and other groups.40–42 Cu-catalyzed borocarbonylation in particular has been successfully demonstrated in diverse π-systems. These reactions generally involve the generation of Cu-Bpin species,43–46 which subsequently undergo addition to unsaturated bonds to afford boryl-alkyl/alkenyl copper intermediate. Then, the copper intermediate is followed by CO (carbon monoxide) insertion and the interception of the electrophile to generate the corresponding carbonyl-containing organoboron compounds. Interestingly, very recently our group reported a Cu-catalyzed carbonylative catenation and borylation of β-substituted styrenes.47 In this protocol, we proposed a carbene species as the key intermediate. Encouraged by this work, we wondered about further applications of this carbene intermediate to achieve selective X–H bond insertion from rather challenging α-substituted styrene substrates to build organoboronates bearing a quaternary carbon center. Herein, we disclose a copper-catalyzed borocarbonylation of α-substituted styrenes via ligand-controlled chemoselective carbene insertion into O–H bonds and C–H bonds. Specifically, with N-heterocyclic carbene (NHC) as the ligand, β-boryl quaternary aldehydes can be formed via carbene insertion into O–H bonds; While using phosphine ligand as the ligand, cyclopropylboronate esters bearing a quaternary carbon center can be obtained via carbene insertion into C–H bonds (Scheme 1b). Experimental Methods General procedure for borocarbonylation of α-substituted styrenes via carbene insertion into O–H bonds A vial (4 mL) was charged with SIMesCuCl (5.0 mol %), B2pin2 (76.2 mg, 1.5 equiv), KOtBu (67 mg, 3.0 equiv), and a stirring bar. The vial was closed by poly(tetrafluoroethylene) (PTFE)/white rubber septum (Wheaton 13 mm Septa) and a phenolic cap and connected with the atmosphere with a needle. The vial was evacuated under vacuum and recharged with argon three times. Then, tetrahydrofuran (THF; 1.0 mL) was injected under argon by using a syringe. After that tBuOH (0.4 mmol, 2.0 equiv) and α-substituted styrenes (0.2 mmol, 1.0 equiv) were added, and the vial (or several vials) was placed in an alloy plate, which was transferred into a 300 mL autoclave of the 4560 series from Parr Instruments (Moline, IL, USA). After flushing the autoclave three times with CO, a pressure of 5 bars of CO was adjusted at ambient temperature. Then, the reaction was performed for 16 h at 80 °C. After the reaction was complete, the autoclave was cooled down with ice water to room temperature, and the pressure was released carefully. The reaction was diluted with ethyl acetate (EA) and filtered through a pad of silica gel (a pipette with about 3 cm silica gel). The filtrate was concentrated under reduced pressure, and the residue was directly purified by column chromatography to afford the corresponding products 4. General procedure for borocarbonylation of α-substituted styrenes via carbene insertion into C–H bonds A vial (4 mL) was charged with 1,2-bis(diphenylphospino)ethane (DPPE) (10.0 mol %), Cu(OAc)2 (10.0 mol %), B2pin2 (101.6 mg, 2.0 equiv), KOtBu (67 mg, 3.0 equiv), and a stirring bar. The vial was closed by PTFE/white rubber septum (Wheaton 13 mm Septa) and phenolic cap and connected with the atmosphere with a needle. The vial was evacuated under vacuum and recharged with argon three times. Then, toluene (1.0 mL) was injected under argon by using a syringe. After that tBuOH (0.2 mmol, 1.0 equiv) and α-substituted styrenes (0.2 mmol, 1.0 equiv) were added, and the vial (or several vials) was placed in an alloy plate, which was transferred into a 300 mL autoclave of the 4560 series from Parr Instruments. After flushing the autoclave three times with CO, a pressure of 5 bar of CO was adjusted at ambient temperature. Then, the reaction was performed for 16 h at 60 °C. After the reaction was complete, the autoclave was cooled down with ice water to room temperature, and the pressure was released carefully. The reaction was diluted with EA and filtered through a pad of silica gel (a pipette with about 3 cm silica gel). The filtrate was concentrated under reduced pressure, and the residue was directly purified by column chromatography to afford the corresponding cyclopropylboronate esters 5. Results and Discussion Our initial optimization studies were conducted with α-methylstyrene 1a using stoichiometric amounts of bis(pinacolato)diboron (B2pin2), KOtBu, tBuOH, and THF as solvent under CO (5 bar) atmosphere at 80 °C. We found that the desired product β-borylated aldehyde 4a could be obtained in 71% gas chromatography (GC) yield when SIMesCuCl was used as the catalyst (Table 1, entry 1). A minor amount of the protoborated 3a formed as the byproduct. Copper catalyst ImesCuCl, IPrCuCl, and SIPrCuCl gave lower yields (18–48% yields, Table 1, entries 2–4), while 1,3-Bis (diphenylphosphino)propane (DPPP)/CuCl instead of ImesCuCl as the catalyst only afforded product 4a in 12% yield (Table 1, entry 5). The use of monodentate ligand PPh3 instead of DPPP as ligand did not generate 4a (Table 1, entries 6). Only byproduct 3a was delivered when KOMe was used as the base, and low yield (17%) of the product 4a was formed with NaOtBu as the base (Table 1, entries 7 and 8). Changing the solvent to CH3CN or N,N-Dimethylacetamide (DMAc) resulted in a trace amount of product 4a (Table 1, entry 9), and 1,4-dioxane only gave 4a in 25% yield (Table 1, entry 10). 38% yield of 4a was obtained when no tBuOH was added showing that a minor amount of water (likely introduced during the weighing process under air or from the reagents) existed in the system (Table 1, entry 11). Using 1.0 equiv of H2O or EtOH instead of tBuOH led to lower yields (Table 1, entries 12 and 13). Increasing the amount of tBuOH to 2.0 equiv gave the best result (78% yield, Table 1, entry 14). Here it is important to mention that due to the poor stability of β-borylated aldehyde 4a on silica, column chromatography should be performed quickly to prevent product decomposition during the purification process. Table 1 | Investigation of Reaction Conditionsa Entry Deviation from the Above Conditions Yield of 4a (%) 1 None 71 2 IMesCuCl instead of SIMesCuCl 48 3 IPrCuCl instead of SIMesCuCl 31 4 SIPrCuCl instead of SIMesCuCl 18 5 DPPP/CuCl instead of SIMesCuCl 12 6 PPh3/CuCl instead of SIMesCuCl Trace 7 KOMe instead of KOtBu Trace 8 NaOtBu instead of KOtBu 17 9 CH3CN, DMAc instead of THF Trace 10 1,4-Dioxane instead of THF 25 11 No tBuOH 38 12 H2O instead of tBuOH 55 13 EtOH instead of tBuOH 58 14 2.0 equiv tBuOH instead of 1.0 equiv 78 (63)b aReaction conditions: 1a (0.2 mmol, 1.0 equiv), B2pin2 (0.3 mmol, 1.5 equiv), tBuOH (1.0 equiv), SIMesCuCl (5.0 mol %), KOtBu (0.6 mmol, 3.0 equiv), CO (5 bar), 80 °C, THF (1.0 mL), 16 h. Yields are determined by GC with hexadecane as an internal standard. bIsolated yield. With the best conditions in hand, we next assessed the generality of this boroformylation reaction under the optimal reaction conditions. As shown in Scheme 2, α-methylstyrenes bearing different electron-rich or electron-deficient groups at the para position were all successfully converted into the desired products 4a–4h in moderate to good yields. -Me and -OMe groups at meta or ortho position also worked well to give 4i–4l in 49–61% yields. Disubstituted α-methylstyrenes also proceeded efficiently to give the corresponding β-boryl aldehydes 4m and 4n in 53% and 41% yields, respectively. Delightfully, the reaction worked smoothly with α-methylstyrenes containing 2,3-dihydrobenzofuran, benzo[d][1,3]dioxole, 1-naphthalene, and 2-MeO-naphthalene, delivering products 4o–4r in reasonable yields. Other α-alkylstyrenes were readily delivered to corresponding products ( 4s– 4x) in moderate yields, including bulky substitutions, such as isobutyl, cyclohexyl. Moreover, the cyclic boroformylated products 4y–4aa were isolated in 48–65% yields. Finally, the boroformylation of α-methylstyrene using a diboron reagent with a six-membered ring instead of B2pin2 provided 4ab in 45% yield. Unfortunately, 4-chloro-α-methylstyrene, 1,1-diphenylethylene, 1-methyl-3H-indene, 3-vinyl-1H-indole, styrene, and 2-methyl-1-pentene did not work under the present conditions. Scheme 2 | Substrates scope.aaReaction conditions: 1 (0.2 mmol, 1.0 equiv), B2pin2 (0.3 mmol, 1.5 equiv), tBuOH (2.0 equiv), SIMesCuCl (5.0 mol %), KOtBu (0.6 mmol, 3.0 equiv), CO (5 bar), 80 °C, THF (1.0 mL), 16 h, isolated yields. Download figure Download PowerPoint Surprisingly, during the screening of the above reaction conditions, we also found that the cyclopropylboronate ester 5a was formed by using phosphine ligands under certain conditions. To our delight, 5a was delivered in 62% yield with 2.5∶1 dr by employing DPPE/CuCl as the catalyst in toluene under 60 °C (Table 2, entry 1). Subsequently, various phosphine ligands were surveyed, such as Xantphos, 1,1-bis(diphenylphosphino)methane (DPPM), DPPP, 1,1′-bis (diphenyphosphino)ferrocene (DPPF), and 1,2-bis(diphenylphosphino)benzene (DPPBz). The yields of the desired 5a could not be further improved (entries 2–6). SIPrCuCl instead of DPPE/CuCl only resulted in a trace amount of 5a (entry 7) whereas SIMesCuCl led to β-boryl aldehyde 4a as the major product (entry 8). Although varying the copper precatalysts had limited impact on yields (Table 2, entries 9 and 10), Cu(OAc)2 was found to give better diastereoselectivity (3:1) and isolated in 58% yield. Table 2 | Investigation of Reaction Conditionsa Entry Deviation from the Above Conditions Yield of 5a (%) dr 1 None 62 2.5∶1 2 Xantphos instead of DPPE <5 / 3 DPPM instead of DPPE Trace / 4 DPPP instead of DPPE 60 1∶1.5 5 DPPF instead of DPPE 9 1.2∶1 6 DPPBz instead of DPPE 37 6∶1 7 SIPrCuCl instead of DPPE/CuCl Trace / 8 SIMesCuCl instead of DPPE/CuCl Traceb / 9 Cu(OAc)2 instead of CuCl 64 (58)c 3∶1 10 CuBr instead of CuCl 61 2.5∶1 aReaction conditions: 1a (0.2 mmol, 1.0 equiv), B2pin2 (0.3 mmol, 1.5 equiv), tBuOH (2.0 equiv), DPPE (10 mol %), CuCl (10 mol %), KOtBu (0.6 mmol, 3.0 equiv), CO (5 bar), 60 °C, toluene (1.0 mL), 16 h. Yields are determined by GC with hexadecane as an internal standard; diastereomeric ratios were determined by 1H NMR analysis. bMajor product was 4a. cIsolated yield. Using the optimized reaction conditions for this carbene insertion into the C–H bond reaction, we evaluated the substrate scope of this methodology. As summarized in Scheme 3, the reaction proceeded smoothly with a variety of α-substituted styrenes, affording the expected cyclopropylboronate esters in moderate yields. α-substituted styrenes bearing either electron-donating or electron-withdrawing groups at the para, meta, and ortho positions of the phenyl ring reacted well to give the products ( 5a–5i) in reasonable yields (41–60%) with indicated diastereomeric ratio (dr) values (1.2∶1–4∶1). The reaction was compatible with α-substituted styrenes containing two substituents on the aromatic ring, 2,3-dihydrobenzofuran, and benzo[d][1,3]dioxole, generating the corresponding products 5j–5m in 43–51% yields. α-Ethyl styrene and exocyclic styrenes were also tolerated under the catalytic system to deliver 5n–5p in 38–52% yields. Notably, the spiro product 5o was formed with outstanding diastereoselectivity (>20∶1 dr). The major diastereoisomers were determined by comparing the NMR spectra with Charette’s48 and Tortosa’s49 work. Scheme 3 | Substrates scope.aaReaction conditions: 1 (0.2 mmol, 1.0 equiv), B2pin2 (0.3 mmol, 1.5 equiv), tBuOH (2.0 equiv), DPPE (10 mol %), Cu(OAc)2 (10 mol %), KOtBu (0.6 mmol, 3.0 equiv), CO (5 bar), 60 °C, toluene (1.0 mL), 16 h; isolated yield; diastereomeric ratios were determined by 1H NMR analysis. Download figure Download PowerPoint To demonstrate the efficiency and practicability of the carbene insertion into O–H bond and C–H bond procedures, scale-up reactions were carried out with a reduced amount of catalyst loading. A 2.5 mol % loading of the copper catalyst was sufficient to perform the reaction on a 3 mmol scale (Scheme 4, I). Despite the reduced amounts of catalyst, 4a was produced in 55% yield (452 mg). Then, a 3 mmol-scale reaction of alkene 1a was also performed with 5.0 mol % CuCl/DPPE, delivering 5a in 50% yield with 2/1 dr. To showcase the synthetic utility of this methodology, some further transformations of product 4a were performed (Scheme 4, II). Oxidation of 4a with NaBO3 generated the β-hydroxy ketone 6 in 81% yield. Suzuki–Miyaura cross-coupling with iodobenzene using 4a as the nucleophile gave 7 in 74% yield. The product 4a was reduced by NaBH4 to afford the boroxole 8 in 86% yield, which also easily underwent oxidation, and Suzuki-Miyaura cross-coupling produced products 9 and 10, respectively. In addition, the cyclopropylboronate ester 5o can be effectively converted into other compounds through a series of derivatizations of the boronic ester group (Scheme 4, III). Arylation was successfully achieved using both palladium-catalyzed Suzuki–Miyaura coupling50 and transition-metal-free coupling51,52 reactions, providing good yields of 11 and 12, respectively. Compound 13 was prepared through an oxidation-benzoylation sequence. Finally, a C–C bond formation was achieved via Zweifel olefination,53 which provided alkene 14 in 63% yield. Scheme 4 | Scale-up reaction and derivatization. (a) NaBO3.4H2O (4.0 equiv), THF/H2O, rt, 5 h. (b) PhI (1.1 equiv), Pd(PPh3)4 (1.0 mol %), K2CO3 (1.5 equiv), N,N-dimethylformamide (DMF)/H2O, 80 °C, 3 h. (c) NaBH4 (2.0 equiv), MeOH, rt, 1 h. (d) NaBO3.4H2O (4.0 equiv), THF/H2O, rt, 3 h. (e) PhI (1.1 equiv), Pd(PPh3)4 (1.0 mol %), K2CO3 (1.5 equiv), DMF/H2O, 80 °C, 2 h. (f) PhBr (1.1 equiv), Pd(OAc)2 (1.0 mol %), RuPhos (1.0 mol %), KOH (3.0 equiv), THF/H2O, 70 °C, 12 h. (g) (I) NaBO3.4H2O (4.0 equiv), THF/H2O, rt, 5 h; (II) BzCl (1.5 equiv), Et3N (3.0 equiv), 4-dimethylaminopyridine (DMAP; 20.0 mol %), dichloromethane (DCM), rt. (h) (i) Furan (1.2 equiv), nBuLi (1.2 equiv), THF, −78 °C, 1 h; (ii) 5o (1.0 equiv), THF, −78 °C, 1 h, then N-bromosuccinimide (NBS; 1.2 equiv), −78 °C, 1 h. (i) (i) C2H3MgBr (4.0 equiv), THF, rt, 0.5 h; (ii) I2 (4.0 equiv), −78 °C, 0.5 h; (iii) NaOMe (8.0 equiv), MeOH, rt, 1 h. Download figure Download PowerPoint To gain insights into the reaction mechanism of the O–H bond carbene insertion. First, we investigated the stoichiometric experiment with intermediate C, which was prepared in situ from α-methylstyrene and Cu-Bpin under 5 bar of CO. Then, intermediate C further reacted with tBuOH and led to the formation of the expected product 4a containing a quaternary center in 26% yield (Scheme 5, I). Instead of tBuOH, deuterium tBuOD was used for the reaction, and 45% aldehyde hydrogen was deuterated. The result revealed that a minor amount of water from the reagents or the air could act as the proton sources as well. Next, deuterated substrates 1g-d2 and 1g-d5 were subjected separately to the reactions under standard conditions, and no significant H/D exchange was observed. Scheme 5 | Scale-up reaction and derivatizations. Download figure Download PowerPoint On the basis of our experimental observations as well as previous studies,47,54–57 a plausible reaction mechanism for O–H bond carbene insertion process is shown in Scheme 6. The (L’)Cu-Bpin species was formed by the reaction of B2pin2 with (L’)CuCl and tBuOK. Subsequent borocupration of the α-substituted styrenes generated the β-boroalkylcopper intermediate A. Next, CO was inserted into the C–Cu bond of intermediate A to afford the acyl-copper intermediate B, which underwent isomerization instantly to the key carbene intermediate C. Then, carbene intermediate C underwent O–H insertion with tBuOH to provide the intermediate D. The β-elimination from D produces 4, releasing the copper alkoxide species for the next catalytic cycle. Some control experiments and deuterium experiments were conducted for investigating the mechanism for the C–H bond insertion procedure (see Supporting Information Figure S1). The plausible mechanisms have been given in the Supporting Information (see Supporting Information Figure S2), and the computational study of the mechanism is ongoing in our lab.58–60 Concerning the selectivity between β-boryl aldehyde and boryl cyclopropane, we believe it is because the reactivity of the carbene intermediate C is tuned by the ligand added. Scheme 6 | Proposed mechanism for O–H bonds carbene insertion. Download figure Download PowerPoint Conclusion We have described a copper-catalyzed carbonylative borofunctionalization of α-substituted styrenes. The reaction proceeds via ligand-controlled selective carbene insertion into O–H and C–H bonds. This reaction provides a general and versatile procedure to synthesize a variety of synthetically useful β-boryl quaternary aldehydes and cyclopropylboronate esters bearing a quaternary carbon center. The formation of a carbene intermediate was proposed as the key step in this transformation. With NHC (IMes) as the ligand, the carbene intermediate reacts with the O–H bond of alcohol. Meanwhile, using phosphine ligand (DPPE) as the ligand, the carbene intermediate undergoes C–H bond insertion. We anticipate that the proposed carbene intermediates derived from this study will find broad applicability in carbonylation and organic chemistry. Supporting Information Supporting Information is available and includes general comments, general procedures, analytic data, and NMR spectra. Disclosures Because of the high toxicity of carbon monoxide, all the reactions should be performed in an autoclave. The laboratory should be well-equipped with a CO detector and alarm system. Conflict of Interest There is no conflict of interest to report. Funding Information The authors appreciate the financial support from DICP (Dalian Institute of Chemical Physics, CAS) and the K.C. Wong Education Foundation (grant no. GJTD-2020-08).

China's goal of achieving carbon neutrality before 2060: experts explain how.

‘We aim to have CO2 emissions peak before 2030 and achieve carbon neutrality before 2060,’ President Xi Jinping so declared at the General Debate of the 75th United Nations General Assembly on 22 September 2020. More than 130 countries globally have proposed their own carbon neutrality goals by 2050 or 2060. Thus, carbon neutrality is a collective effort of human societies to cope with the climate crisis. If all countries could follow their own plans and reach carbon neutrality in a few decades, we may have a chance to control global warming within 1.5 or 2oC, confining climate change to a relatively safe zone. As a developing country with a large population, high coal consumption and large manufacturing industries, can China achieve the huge task of societal transformation that will enable carbon peaking and carbon neutrality within the next four decades? How will China transform traditional power generation and manufacturing industries, as well as create new technologies for carbon capture and storage? In this panel discussion chaired by Prof. Xinhe Bao, a scientist of energy and chemistry, top experts gathered to discuss the challenges and potential solutions, outlining the coming ‘green industrial revolution’. Huiming Cheng Professor, Institute of Metal Research, Chinese Academy of Sciences; Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences Zhengtang Guo Professor, Institute of Geology and Geophysics, Chinese Academy of Sciences Yaling He Professor, School of Energy and Power Engineering, Xi’an Jiaotong University Zheng Li Professor, Institute of Climate Change and Sustainable Development, Tsinghua University Minggao Ouyang Professor, School of Vehicle and Mobility, Tsinghua University Zhengrong Shi Professor, College of Energy and Mechanical Engineering, Shanghai University of Electric Power Zaiku Xie Professor, China Petroleum and Chemical Corporation (SINOPEC) Xinhe Bao (Chair) Professor, University of Science and Technology of China, and Dalian Institute of Chemical Physics, Chinese Academy of Sciences

Conceptual design of DALS test facility cryogenic system

Dalian advanced light source (DALS) is a new project proposed by Dalian Institute of Chemical Physics (DICP) aiming to produce high-quality electron beam with repetition rate up to 100 kHz and the project is subject to central government approval. The cryomodules and superconducting cavities need to be tested before assembled in the real accelerator so the test facility is necessary. The Accelerator module test facility (AMTF) project has been funded by Dalian local government and is currently under construction as the pre-research project for DALS, it consists of four testbenches, one Horizontal testbench (HTB) for cryomodule test, one Vertical testbench (VTB) for cavity test, one Cryogenic testbench (CTB) for cryogenic test and one Injector testbench (ITB) for beam test. A Test facility cryoplant (TFCP) with capacity of 370 W@2 K will be used for cooling testbenches. This paper presents the design and current progress of the TFCP system, which includes the refrigerators, helium compressors, process vacuum pump system (PVPS), gas storage system, recovery and purification system.

Opportunities and future directions for photocatalytic biomass conversion to value-added chemicals

In this Activity article, Feng Wang (professor at the Dalian Institute of Chemical Physics) and Haohong Duan (associate professor at Tsinghua University) discuss the opportunities for photocatalytic biomass conversion and look at future directions associated with the practical applications. In this Activity article, Feng Wang (professor at the Dalian Institute of Chemical Physics) and Haohong Duan (associate professor at Tsinghua University) discuss the opportunities for photocatalytic biomass conversion and look at future directions associated with the practical applications.

Opportunities for electrocatalytic biomass valorization

In this Activity article, Haohong Duan (associate professor at Tsinghua University) and Feng Wang (professor at the Dalian Institute of Chemical Physics) introduce the electrocatalytic strategy for biomass valorization and discuss the opportunities and challenges associated with its practical applications.

A Risk Model Including Eight Tumor Microenvironment-Related Genes for Prediction of Lung Adenocarcinoma Prognosis

Background: The tumor microenvironment (TME) plays a crucial role in lung cancer development and outcome. The objective of this study was to construct a prognostic model using TME-related genes. Methods: The Cancer Genome Atlas (TCGA) and Gene Expression Omnibus (GEO) provided transcriptome profile and clinical characteristics. We examined and selected the key genes to obtain a predictive risk model for lung adenocarcinoma (LUAD) prognosis. We also assessed the efficiency of the model and the interaction of key genes with immune-related genes. Findings: After screening 760 TME-related genes, we established a risk model using ANGPTL4, FUT4, CDC25C, FLNC, KRT6A, NEIL3 , HS3ST2, and DAAM2 to independently predict LUAD prognosis using TCGA data. The ROC curve and C-index confirmed the usefulness of this risk model, and a nomogram that integrated this predictive risk model with age and TNM stages was more effective on prediction of LUAD prognosis. The risk model was further confirmed using the GEO data. Furthermore, the risk model of genes interacted with 11 types of immune cells and three immune checkpoint proteins (LAG3, PDL1 and TDO2) in LUAD. Interpretation: Our predictive risk model was effective on survival prediction and helpful for immune targeted therapy in LUAD patients. Funding Information: This study was supported in part by grants from the National Natural Science Foundation of China (#81703087, #81903185, and #81972916), the United Fund of the Second Hospital of Dalian Medical University and Dalian Institute of Chemical Physics, Chinese Academy of Sciences (#UF-ZD-202011), and Project of Education Department of Liaoning Province (#LZ2020009). Declaration of Interests: The authors declared that there is no conflict of interest in this work. The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

Zhao Li

ChemCatChemVolume 12, Issue 17 p. 4255-4256 InterviewFree Access Zhao Li First published: 18 August 2020 https://doi.org/10.1002/cctc.202001156AboutSectionsPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Graphical Abstract Zhao Li See the Very Important Paper in our Young Researchers Series at https://doi.org/10.1002/cctc.202000715 Date of birth: August 9, 1987 Position: Postdoc at Department of Chemistry, University of Toronto, Toronto (Canada) E-mail: [email protected] Education: Chemistry, Inner Mongolia University, Hohhot, China (2006—2010) PhD, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China, under the supervision of Prof. Ping Chen (2010–2017) Postdoctoral position at the Department of Chemistry, University of Toronto, Toronto, Canada, with Prof. Geoffrey Ozin (2018–now) Awards: Merit student of the Chinese Academy of Sciences. Yanchang Petroleum Excellent Doctoral scholarship. National scholarship for undergraduate students. Current research: Our research focus on catalytic conversion of carbon dioxide into value-added chemical fuels by using solar energy to tackle global warming and energy crisis; with an special interest in the design of high efficient catalysts, examining the mechanism on surface of the catalyst and the relationship between light and activity. Hobbies/Interests: Travel and cooking. The thing I like most about my work is exploring unknown catalysts in reactions or finding new perspectives to explain the mechanisms. I would like to have a year off to travel around the world. My motto is: “Tomorrow is another day.” If I could go back in time and do any experiment, it would be the hardest time during my PhD and persuade myself to try every possibility. My favorite time of day is the late night which facilitates to calm down and contemplate. What aspects of your research do you find most exciting? The most exciting thing in my research is developing new ideas based on the work of the pioneers and investigating own's ideas in reactions. For example, the galvanic replacement has been developed for many years. When I read the related papers, I envisioned that the bimetallic catalyst could be synthesized by this method with controlled morphologies and compositions. Then the single atom alloys and hollow-structure alloys were successfully prepared with full utilization of noble metals according to this prediction. Realizing own's ideas gives us positive feedback and helps to build up confidence, and then drives us to continue exploring unknown future. Is your current research mainly curiosity driven (fundamental) or rather applied? In my opinion, fundamental as well as applied research are both important, especially regarding our catalysis. Many classical reactions such as the Haber-Bosch and the Fischer–Tropsch processes are the foundation of chemical industry. Although they have developed maturely, there are a lot of problems that still need to be improved, which also bring us opportunities and challenges. To meet the requirements for industrial application, we can rationally design our experiments with the specific targets. In turn, more details and mechanisms are easier to investigate from a fundamental side. Now, I try to use solar energy to drive the Fischer–Tropsch process by substituting CO with CO2, which is a good project to combine fundamental and applied research. Who has been your biggest influence? My PhD supervisor Prof. Ping Chen, professor and division head of Hydrogen Energy and Advanced Materials, Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences (China), sets a good example for me. She was the first one to bring me to the scientific research and opened the door of the fantastic catalysis for me. As a female scientist, she totally understood and encouraged me to insist on my research. She taught me how to think and investigate the questions from a new perspective and challenge the classic experiences and theories, which are key qualities for young scientists. I also learned from her how to balance life and work. My 3 top papers: 1“Atomically dispersed Pt on Ni nanoparticles – synthesis and catalytic function in hydrogen generation from aqueous ammonia–borane ”: ACS Catal. 2017, 7, 6762–6769. Herein, we used a simple method to synthesize a single atom alloy, which exhibits high catalytic performance in the hydrolysis of ammonia borane. 2“Covalent triazine framework supported non-noble metal nanoparticles with superior activity for catalytic hydrolysis of ammonia borane: from mechanistic study to catalyst design”: Chem. Sci. 2017, 8, 781–788. Herein, we reported on the rational design of electron-rich catalysts with high activity in the hydrolysis of ammonia borane. 3“ Syntheses of Pt-Ni hollow nanoalloy for hydrogen generation from catalytic hydrolysis of ammonia borane“: ChemCatChem 2020, 12, 4257–4261. Herein, we report on a simple method to synthesize bimetallic catalysts with hollow structures, which exhibit high catalytic performance in the hydrolysis of ammonia borane. Volume12, Issue17September 4, 2020Pages 4255-4256 This article also appears in:Young Researchers Series ReferencesRelatedInformation

Emerging Nanomaterials for Light‐Driven Reactions: Past, Present, and Future

Solar RRLVolume 4, Issue 8 2000354 EditorialFree Access Emerging Nanomaterials for Light-Driven Reactions: Past, Present, and Future Wee-Jun Ong, Corresponding Author Wee-Jun Ong weejun.ong@xmu.edu.my orcid.org/0000-0002-5124-1934 School of Energy and Chemical Engineering, Xiamen University Malaysia, Selangor Darul Ehsan, 43900 Malaysia College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 ChinaSearch for more papers by this authorKazuhiko Maeda, Corresponding Author Kazuhiko Maeda maedak@chem.titech.ac.jp School of Science, Tokyo Institute of Technology, 2-12-1-NE-2 Ookayama, Meguroku Tokyo, 152-8550 JapanSearch for more papers by this author Wee-Jun Ong, Corresponding Author Wee-Jun Ong weejun.ong@xmu.edu.my orcid.org/0000-0002-5124-1934 School of Energy and Chemical Engineering, Xiamen University Malaysia, Selangor Darul Ehsan, 43900 Malaysia College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 ChinaSearch for more papers by this authorKazuhiko Maeda, Corresponding Author Kazuhiko Maeda maedak@chem.titech.ac.jp School of Science, Tokyo Institute of Technology, 2-12-1-NE-2 Ookayama, Meguroku Tokyo, 152-8550 JapanSearch for more papers by this author First published: 11 August 2020 https://doi.org/10.1002/solr.202000354Citations: 1AboutSectionsPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat In 2020, the global energy consumption is anticipated to surpass 14 gigatons oil equivalent (5.8 × 1020 J).[1] To maintain the growth of high energy demand from the increasing global population and rapid industrial development, the consumption of energy is going to accelerate year by year. With the increasingly serious environmental contamination and global energy crisis, the development of clean and renewable energy has captivated interest among researchers and scientists to circumvent the worldwide challenges facing human beings at present. Among all forms of renewable energy, solar energy is an inexhaustible source of clean energy. The amount of solar energy reaching the earth is as high as 4 × 106 EJ per year, of which 5 × 104 EJ is deemed to be easily harvestable. Although people are gradually realizing the vast potential of solar energy, its current contribution to global energy is still below par. At present, how to efficiently harvest solar absorption as well as the development of flexible displays in solar technologies still markedly hinder practical industrialization and commercialization. As a result, novel fundamental understanding and practical techniques for solar technologies are of utmost significance to serve as a paradigm for solar technological readiness. This special issue of Solar RRL, “Nanomaterials for Light-Driven Reactions” encompasses 2 Progress Reports, 8 Reviews, 4 Communications, and 15 Full Papers by renowned research groups working at Nanyang Technological University, National Institute for Materials Science, Dalian Institute of Chemical Physics, Xiamen University Malaysia, Jawaharlal Nehru Centre for Advanced Scientific Research, Tianjin University, University of Bayreuth, Ulsan National Institute of Science and Technology, Université de Picardie Jules Verne, Ben Gurion University of the Negev, and so forth. The Special Issue highlights emerging works on the topics of various light-driven reactions using advanced nanomaterials (Figure 1). To date, substantial achievements have been devoted to the realm of light-driven reactions for attaining high-efficiency photocatalysis, photoelectrocatalysis, photovoltaics, solar cells, and bio-photoelectrochemical reactions, thus giving impetus to the breakthrough advancement in the field of solar technologies. In particular, a diverse range of advanced nanomaterials such as metal-free graphitic carbon nitride, metal, metal oxide, metal phosphide, metal dichalcogenide, metal nitride, perovskite, MXene, and metal-organic frameworks in a myriad of structures and morphologies such as nanosheets, nanowires, nanorods, nanocubes, and porous architectures have been discussed in these invited articles. Figure 1Open in figure viewerPowerPoint Summary of major research works presented in the special issue “Nanomaterials for Light-Driven Reactions” guest-edited by Prof. Wee-Jun Ong and Prof. Kazuhiko Maeda in Solar RRL. Shen et al. have provided a progress report on the synergy of low dimensionality and heterostructure design for graphitic carbon nitride (g-C3N4)-based heterostructures to modulate physicochemical properties (e.g. electronic band structure, increased visible light absorption, enhanced photoinduced charge carrier separation) and their application for water splitting, CO2 reduction, and pollutant degradation (1900435). Ong's group has recently reviewed the state-of-the-art development of 2D/2D heterostructured photocatalysts as an emerging platform for artificial photosynthesis by elucidating the interplay of 2D/2D heterojunction interfaces and the associated charge properties toward the photocatalytic enhancement in water splitting, CO2 reduction, and N2 fixation (2000132). Rao's group presented a variety of 2D catalysts, including transition metal dichalcogenides, carbon nitride, heterostructures, and covalently cross-linked 2D composites, for photocatalytic water splitting (2000050). Other than water splitting, Sun et al. systematically reviewed metal-free photocatalysts for CO2 reduction and discussed the theoretical calculations on possible reduction mechanisms and pathways as well as the in situ and operando techniques for mechanistic understanding (1900546). Zhang and co-workers provided an overview of oxygen vacancies in semiconductive metal oxides, including their emerging roles, fabrication techniques, characterizations, and photocatalytic applications (2000037). Additionally, Xu et al. focused on the effects of surface/interface engineering of carbon-based materials in versatile systems for enhanced applications in emerging solar energy conversion and storage (1900577). Moreover, Ye et al. reviewed the recent progress of high-stability metal–organic frameworks (MOFs) for photocatalytic solar fuel production (1900547). In another review, Zhang et al. summarized the recent advances of photoelectrodes based on pure organic materials, such as polythiophenes, graphitic carbon nitrides, conjugated acetylenic polymers, and N-containing fused-ring small molecules, for water splitting (1900395). Apart from pristine organic materials, Wang's group presented a review on metal oxide photoanodes for photoelectrochemical (PEC) water oxidation by describing effective enhancement strategies such as the construction of nanostructures, introduction of dopants, control of crystal facets, design of heterojunctions, modification of interfaces, and the integration of multiple strategies (1900509). The last review article of this special issue came from Wang's group at Soochow University, China, who highlighted the current endeavor to achieve low-temperature flexible perovskite solar cells (FPSCs). Particularly, the methods for ameliorating the stability and flexibility of FPSCs were presented by taking into account of the electrode materials, device encapsulation, and structural effects (1900556). Over the past few years, there have been a plethora of research works focusing on g-C3N4 for water splitting. Wang et al. have successfully doped phosphorus (P) into polymeric g-C3N4 (PCN) films through in situ polymerization process, which enhanced the ability of water oxidation owing to increased valence potential of P-doped PCN as compared to the undoped one (2000168). Other than water oxidation, Tang's group employed a series of visible-light-responsive Ce-UiOs developed through metal substitution and ligand modification for the application in aerobic oxidation of benzyl alcohol (1900449). In another similar application on the organic transformation, Sauvage et al. loaded gold nanoparticles on large bandgap semiconductor CeO2 under simulated sunlight irradiation for aerobic oxidation of free sugars. The enhancement stemmed from a thermal activation process induced by near-infra-red (NIR) light rather than the plasmonic contribution of Au nanoparticles (2000084). Feng et al. reported a high-performance PEC bioassay system based on the PEC and oxidase-catalytic coupled reactions at an air–liquid–solid triphase joint interface, which could be generalized to construct high-performance PEC bioassay systems for accurate analyte determination (1900185). As is widely known, water splitting for hydrogen (H2) and oxygen (O2) evolution has been extensively studied for the past decade. In particular, H2 is appealing to serve as a clean energy since it represents a chemical fuel with the highest energy density (140 MJ kg−1) on a gravimetric basis. Shalom's group utilized sulfur-based supramolecular assemblies composed of bismuthiol and melamine to synthesize ordered carbon nitride for excellent photocatalytic H2 evolution apart from the degradation of rhodamine B dye (2000017). Motivated by large interfacial contact area in ultrathin 2D/2D heterojunction interfaces, Xu et al. integrated 2D Ni(OH)2 as an operational cocatalyst with 2D g-C3N4 for photocatalytic H2 evolution without using Pt cocatalysts (1900538). In another similar work, Li et al. fabricated cocatalyst-free 2D/2D CdS/g-C3N4 step-scheme (S-scheme) heterojunction photocatalysts via in situ hydrothermal route, which manifested excellent H2 production with an apparent efficiency of 6.9% at 420 nm (1900423). Other than the development of binary photocatalysts, Li et al. have successfully constructed ternary nanostructure photocatalysts via a self-sacrificial strategy by forming a hierarchical architecture of In(OH)3 nanocubes decorated NiS-ZnIn2S4 (ZIS) hybrid nanosheets (ZIS/In(OH)3-NiS). Interestingly, the H2 generation rate was by far one of the highest among ZnIn2S4-based photocatalysts reported to date, which will provide a valuable reference to comprehend the structure-determining properties of nanohybrid architecture (2000027). Furthermore, Chen's group has electrodeposited Ni–M (M = Co, Fe, Mo) as a surface catalyst onto p-type silicon micropillar arrays for solar-driven hydrogen evolution. More importantly, the incorporation of high-valence Mo species as a key promoter for the in situ formation of active Ni2+ species on the surface of alloys was successfully evidenced, which was crucial to demystify the dynamic electronic and atomic structures of highly active surface catalysts (2000028). By means of first-principles density functional theory (DFT) simulations, Chen et al. have surveyed the solar catalytic activity toward hydrogen evolution reaction for all low-index surfaces of dissimilar nickel phosphides (Ni3P, Ni12P5, Ni2P, Ni5P4, NiP, NiP2, and NiP3) (1900360). Very recently, there has been a driving force to investigate the O2 evolution from another half-reaction of water splitting. For example, Xu et al. demonstrated that 2D MXene (Ti3C2) with high electron conductivity functioned as a robust electron transfer and transport medium after being hybridized with Ag3PO4 for effective photocatalytic O2 generation (1900434). In another work, Zhang et al. adopted foreign Sc atoms with identical ionic radius to Ta atoms to modulate the structure and photocatalytic activity of Ta3N5. The synergy of Sc doping and CoOx cocatalysts on the promotion of charge separation and surface catalysis, respectively, facilitated the O2 generation in Ta3N5 (1900445). Besides that, Lee's group incorporated Ti4+ and Sn4+ into Fe3+ sites of ZnFe2O4 photoanodes as electron donors, in which the intentional external doping accelerated charge migration with boosted charge carrier density to enhance the bulk charge separation efficiency for photoelectrochemical water splitting (1900328). On top of that, Marschall's group has successfully developed phase-pure and highly crystalline CaFe2O4 with a sponge-like macroporous structure for improved H2 generation as well as overall water splitting upon the deposition of Rh/CrOx (1900570). Recently, g-C3N4 has been employed as robust photocatalysts for CO2 reduction. For instance, Yu's group presented a facile engineering of nanocage g-C3N4 using supramolecular complexes of melamine and cyanuric acid with strengthened hydrogen bonding, which were treated under freeze-drying, for boosted CO2 adsorption and reduction. This interesting work serves as a protocol for modulating the microstructure of g-C3N4 through tuning the weak intermolecular interaction (1900469). Not only that, Maeda's group has synthesized copolymerized carbon nitride nanosheets by heating a mixture of urea and 2-aminobenzonitrile for the visible-light CO2 reduction to formate with the aid of a ruthenium (II) complex catalyst (1900461). In another work, Liu et al. dispersed metallic molybdenum dioxide (MoO2) cocatalysts on g-C3N4 nanosheets to construct a Schottky junction photocatalyst, hence ameliorating the charge transfer and separation for the production of CO from the CO2 reduction (1900416). By mimicking the natural photosynthesis, Wong's group constructed ternary g-C3N4/ZnNCN@ZIF-8 hybrid photocatalysts with robust interfacial interactions via Zn-N bonding to enhance CO2 conversion efficiency, which stemmed from the synergistic contributions of g-C3N4/ZnNCN interfacial Z-scheme heterostructuring and surface-passivated ZIF-8 grafting (1900440). In addition to photocatalytic energy conversion in water splitting and CO2 reduction, Ho et al. exploited a g-C3N4/TiO2 composite hydrosol, in which the TiO2 hydrosol acted as a source of photocatalyst and dispersant for g-C3N4, for air-purifying pavement, thus offering a viable catalyst for environmental remediation (2000170). In short, the collection of invited papers highlights the latest advances in engineering nanomaterials for light-drive reactions based on numerous technological and scientific aspects. We are confident that the mesmerizing breadth of nanomaterials for light-driven reactions published in this Special Issue will inspire immense enthusiasm among researchers in solar energy across the globe. We anticipate that they will draw considerable attention to the field of solar technologies, hence populating concerted efforts toward high-efficiency, robust stability, cost-effective, and environmentally friendly solar technologies in years to come. Lastly, we sincerely thank the Editor-in-Chief of Solar RRL, Dr. Stefan Hildebrandt and the entire editorial team for providing us the opportunity to lead and publish this Special Issue to cast a new epoch for the exploration of solar technologies as an alternative to the conventional fossil fuels. We are grateful to all invited authors and reviewers for their contributions. This would not have been successful without the untiring support and dedication from everyone. Acknowledgements W.-J.O. acknowledges financial assistance and start-up grants from Xiamen University Malaysia. This work was supported by Xiamen University Malaysia Research Fund (XMUMRF/2019-C3/IENG/0013). Biographies Wee-Jun Ong received his B.Eng. and Ph.D. in chemical engineering from Monash University. He is an Associate Professor in School of Energy and Chemical Engineering at Xiamen University Malaysia. Previously, he was a staff scientist at Agency for Science, Technology and Research (A*STAR), Singapore. In 2019, he was a visiting scientist in Professor Xinliang Feng's group at Technische Universität Dresden, Germany. In 2019, he was a visiting professor at Lawrence Berkeley National Laboratory, USA. His research interests include the design of nanomaterials for photocatalytic, photoelectrocatalytic, and electrochemical H2O splitting, CO2 reduction, and N2 fixation. For more details, refer to https://sites.google.com/site/wjongresearch/. Kazuhiko Maeda received his Ph.D. degree from The University of Tokyo (2007) under the supervision of Professor Kazunari Domen. During 2008–2009, he was a postdoctoral researcher at Pennsylvania State University, where he worked with Professor Thomas E. Mallouk. In 2009, he joined The University of Tokyo as an Assistant Professor. Moving to the Tokyo Institute of Technology in 2012, he was promoted to an Associate Professor. His research interests include water splitting and CO2 reduction using photocatalysts and photoelectrodes. For more details, refer to http://www.chemistry.titech.ac.jp/~ishitani/member/kmaeda/Home.html. References 1 Statistical Review of World Energy, https://www.bp.com/en/global/corporate/energy-economics/statistical-review-of-world-energy.html (accessed: July, 2020). Citing Literature Volume4, Issue8Special Issue: Nanomaterials for Light-Driven ReactionsAugust 20202000354 FiguresReferencesRelatedInformation

The Power of Hydrides

Qianru Wang is a graduate student pursuing her Ph.D. in physical chemistry at Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Her research focuses on hydride materials for catalytic ammonia synthesis. Jianping Guo is a professor at Dalian Institute of Chemical Physics, Chinese Academy of Sciences. His research focuses on exploring metal hydrides, imides, and amides in the activation and transformation of small molecules including N2, H2, and NH3. Ping Chen is a professor and division head of Hydrogen Energy and Advanced Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. The primary research interests of her group include materials development for hydrogen storage and catalysis.

Dalian Institute of Chemical Physics (Adv. Mater. 50/2019)

Advanced MaterialsVolume 31, Issue 50 1970350 Cover PictureFree Access Dalian Institute of Chemical Physics (Adv. Mater. 50/2019) First published: 10 December 2019 https://doi.org/10.1002/adma.201970350AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat Graphical Abstract This special issue on advanced materials for clean energy celebrates the 70th anniversary of Dalian Institute of Chemical Physics. The front cover shows a top-view panorama of Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Volume31, Issue50Special Issue: DICP's 70th Anniversary Special Issue on Advanced Materials for Clean EnergyDecember 13, 20191970350 RelatedInformation

History of the Dalian Institute of Chemical Physics and the Friendship between China and Japan in catalysis

This article presents a history of the origins of the Dalian Institute of Chemical Physics, Chinese Academy of Sciences (Abbreviated as DICP) and relates the recent friendship between China and Japan in the field of catalysis. Although the official beginning of DICP is in 1949 with the birth of the People's Republic of China, there are earlier roots that went back to the defeat of Russia by Imperial Japan in 1905. This began a period of occupation and exploitation of Northest Asia by Japan which did not end until its defeat by Allied forces in 1945. During the period of occupation, a laboratory was created called the Central Research Laboratory of the South Manchurian Railroad Company, which was staffed by the best and brightest researchers from Japan, and was able to develop new processes in chemicals and synthetic fuels that fed the Japanese Imperial forces. Between 1945 and 1949, Dalian was administered by the Soviet Union, and the removable equipment from the Laboratory was taken. In this period one individual stood out, the Laboratory Director Marusawa Tsuneya, who risked his life to preserve the scientific records and staff of the institute, and then stayed in Dalian for ten years after the Second World War to help China rebuild its capabilities. The Central Research Laboratory is still preserved as the Old Campus of DICP. The origin of the friendship between China and Japan in catalysis can be traced to Professor Morikawa Kiyoshi, who worked in the Central Research Laboratory and helped commercialize a shale coal liquefaction process. Upon his return to Japan he became Professor at the Tokyo Institute of Technology and in 1975 organized the first visit by Japanese academics to China. This was reciprocated in visits to Japan in 1977 and 1980 by top researchers such as Zhang Dayu, Min Enze, Tsai Khirui, Lu Jiaxi, and Lin Liwu. This resulted in numerous contacts between individuals, which multiplied geometrically. Notably among these were the personal interactions between Guo Xiexian, the Vice-Director of DICP and Tamaru Kenzi, a Professor at the University of Tokyo, which led to a friendship lasting decades and encompassing generations. In 1981, Guo Xiexian organized the first China-Japan-USA Symposium in Dalian, assisted by Tamaru Kenzi, which was attended by over 90 scientists. This meeting was a big success, and was to lead to the organization of many other multi-country conferences, further promoting exchanges. It culminated with the hosting of China of the 16 th International Congress on Catalysis in 2016 in Beijing, with Li Can as President. Today DICP is a sprawling organization with over 1300 permanent staff, and is one of the powerhouses of catalysis in the world. From 2000, it has been led by Directors Bao Xinhe, Zhang Tao, and Liu Zhongmin. The Institute is making enormous contributions to research and producing cutting-edge technology, and its future is bright. The year 2019 marks the 70 th anniversary of the beginning of the Dalian Institute of Chemical Physics, Chinese Academy of Sciences (DICP). This article presents a history of the origins of DICP and relates the recent friendship between China and Japan in the field of catalysis.

Catalyst: Single-Atom Catalysis: Directing the Way toward the Nature of Catalysis

Xuning Li is a research fellow at Nanyang Technological University (NTU). He earned his PhD at Dalian Institute of Chemical Physics (DICP) in 2017. His current research interest focuses on in situ/operando characterization techniques in single-atom catalysis. Yanqiang Huang received his PhD from DICP in 2008. Afterward, he joined DICP as a staff scientist and was promoted to full professor in 2016. His research interests include propellant catalytic decomposition, CO2 capture and utilization, and C1 chemistry. Bin Liu received his PhD from the University of Minnesota (2011) and then moved to the University of California, Berkeley, as a postdoctoral researcher (2012). He is now an associate professor at NTU. His main research interests are electrocatalysis, photovoltaics, and photo-electrochemistry.

Preface to Special Issue on Celebrating the 70th Anniversary of Dalian Institute of Chemical Physics, Chinese Academy of Sciences

Preface to Special Issue on Celebrating the 70th Anniversary of Dalian Institute of Chemical Physics, Chinese Academy of Sciences

Recent Progress in Methanol-to-Olefins (MTO) Catalysts.

Methanol conversion to olefins, as an important reaction in C1 chemistry, provides an alternative platform for producing basic chemicals from nonpetroleum resources such as natural gas and coal. Methanol-to-olefin (MTO) catalysis is one of the critical constraints for the process development, determining the reactor design, and the profitability of the process. After the construction and commissioning of the world's first MTO plant by Dalian Institute of Chemical Physics, based on high-efficiency catalyst and fluidization technology in 2010, more attention has been attracted for a deep understanding of the reaction mechanism and catalysis principle, which has led to the continuous development of catalysts and processes. Herein, the recent progress in MTO catalyst development is summarized, focusing on the advances in the optimization of SAPO-34 catalysts, together with the development efforts on catalysts with preferential ethylene or propylene selectivity.

A Comprehensive Review Covering Conventional and Structured Catalysis for Methanol to Propylene Conversion

The conversion of methanol to propylene is a value-added process and has gained extreme significance because of high demand for propylene in the production of petrochemicals. The demand for propylene is increasing due to increasing usage of polypropylene. During the last two decades, propylene demand growth has far overtaken ethylene demand growth and it is predicted to be more than double in the next 20 years. The Dalian Institute of Chemical Physics has been working for the last three decades in the R&D of the methanol to olefins reaction and have developed MTP technology. The catalytic materials used in methanol to propylene conversion include SAPO-34 (small-pore molecular sieves), ZSM-5 (medium-pore zeolites) and its modified forms. Limited research has also been done using large pore zeolites such as mordenite and beta. High-silica EU-1 zeolite has been found as an efficient catalyst for MTP conversion. The use of SAPO-18, ZSM-23 and CON-type zeolite for MTP reaction has also been discussed. Methanol to propylene research has been carried using structured catalysts including ceramic based honeycomb or monolith and silicon carbide foam. The major difference in process design between SAPO-34 and H-ZSM-5 is that the SAPO-34 is used in fluidized bed process while H-ZSM-5 catalyst is used in fixed bed process. SAPO-34 is a selective catalyst for olefins but deactivates fast and thus requires frequent regeneration. The H-ZSM-5 is less selective for olefins but shows less deactivation and thus quite stable. A number of structured supports such as monolith, foam, and mesh have been researched for coating with the active zeolite based catalysts. The structured catalysts have the advantage to reduce the diffusional limitations of pellet catalyst system and have exhibited excellent results in terms of activity and selectivity for olefins as well as in reducing aromatics formation. The results obtained in our research using zeolite coated structured catalysts have shown significant increase in propylene selectivity. The significant findings of our work has been published and patented with US Patent and Trademark Office (USPTO).

Dalian Institute of Chemical Physics, Chinese Academy of Sciences.

Dalian Institute of Chemical Physics, Chinese Academy of Sciences.

In-situ growth of vertically aligned nickel cobalt sulfide nanowires on carbon nanotube fibers for high capacitance all-solid-state asymmetric fiber-supercapacitors

Fiber-supercapacitors (FSCs) are promising power sources for miniature portable and wearable electronic devices. However, the development and practical application of these FSCs have been severely hindered by their low volumetric capacitance and narrow operating voltage. In this work, vertically aligned nickel cobalt sulfide (NiCo 2 S 4 ) nanowires grown on carbon nanotube (CNT) fibers were achieved through an in-situ two-step hydrothermal reaction method. The as-prepared NiCo 2 S 4 @CNT fiber electrode exhibits a high volumetric capacitance of 2332 F cm−3, benefiting from its superior electric conductivity, large surface area, and rich Faradic redox reaction sites. Furthermore, a NiCo 2 S 4 @CNT//VN@CNT (vanadium nitride nanosheets grown on CNT fibers) asymmetric fiber-supercapacitor (AFSC) was successfully fabricated. The device exhibits an operating voltage up to 1.6 V and a high volumetric energy density of 30.64 mWh cm−3. The device also possesses outstanding flexibility as evidenced by no obvious performance degradation under various bending angles and maintaining high capacitance after 5000 bending cycles. This work promotes the practical application of flexible wearable energy-storage devices. © 2019 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences

The past and future of USTC: an interview with USTC President Xinhe Bao.

The University of Science and Technology of China (USTC) is located in Hefei, the capital of Anhui province, and has its own characteristics among the universities in China. Established by the Chinese Academy of Sciences (CAS), USTC is distinctively tinted with a scientific color. It is also famous for its ‘Special Class for the Gifted Young’ and is considered one of the best Chinese universities in the fields of science and technology (S&T). Recently, National Science Review interviewed Professor Xinhe Bao, the President of USTC, about the characteristics of the university and the education and research in China. Xinhe Bao is an academician of CAS and has made seminal contributions in catalysis and energy chemistry in the past decades. Before joining USTC, he had worked at Dalian Institute of Chemical Physics (DICP), CAS and Fudan University (Shanghai), and thus possesses an in-depth understanding of the education and research in China.

Selective Cleavage of C-O Bonds in Lignin Catalyzed by Rhenium(VII) Oxide (Re2 O7 ).

Invited for this month's cover are the collaborating groups of Dr. Changzhi Li from Dalian Institute of Chemical Physics, China, and Dr. Lican Lu, Xiangtan University, China. The cover picture shows the harvest of a renewable supply of aromatic compounds accessible from lignin model compounds and lignin feedstocks through the selective Re2 O7 -catalyzed cleavage of lignin C-O bonds. This study paves the way towards the development of rhenium-based catalysts for the reductive valorization of realistic lignin materials in a controlled manner. Read the full text of the article at 10.1002/cplu.201700547.