Bridge Bonds Research Articles

BH6+: Revisiting borohydride cation with negatively charged boron and its possible implications for hydrogen storage

Boron is usually an electropositive element and its hydrides are known for unusual bonding with excellent hydrogen storage capacity. In this paper, we reinvestigated a borohydride cation, BH6+ using the state-of-the-art DFT and ab initio methods. We noticed that its global minimum structure has two covalent 2c-2e bonds and two polar 3c-2e bonds as revealed by the QTAIM analysis. It has indeed negatively charged boron as verified by various population schemes. ADMP simulation-based trajectory analysis of BH6+ for 40 ps confirmed that this cation is kinetically stable over a wide range of temperatures from 100 to 500 K. The superatomic feature of the BH6+ cluster has also been revealed. We also notice that the addition of electrons to BH6+ leads to its dehydrogenation. This may implicate its possible application in high-capacity hydrogen storage.

Nano-photosensitizers with gallic acid-involved Fe–O–Cu “electronic storage station” bridging ligand-to-metal charge transfer for efficient catalytic theranostics

NH2-MIL-88B (Fe) (MOF) is a promising photocatalytic material for antitumor therapy because of its distinctive electronic structure. However, inadequate separation of photo-generated electrons and slow reaction rate in low/high-valence iron (Fe) cycles limit their clinical application. In the present study, “electronic storage station” as a ligand-to-metal charge transfer bridge bond was constructed to inhibit recombination of electron/hole under 650 nm laser irradiation. Cupric (Cu) ions and gallic acid (GA) were self-assembled into a MOF (denoted as CGMOF) to create an FeO(GA)Cu bridge bond. GA, characterized by robust electron delocalization and abundant electron-donating groups, significantly enhances electron transfer efficiency for photodynamic therapy (PDT). CGMOF can respond to endogenous glutathione and release cuprous ions, accelerating the iron ion/ferrous ion cycles for chemodynamic therapy (CDT). The released Fe species can serve as T2-weighted magnetic resonance imaging contrast. Extended X-ray absorption fine structure spectra confirmed the presence of GA-containing FeOCu bonds in CGMOF. Furthermore, a series of photo-electrochemical tests confirmed that the formation of FeO(GA)Cu bond prominently elevated the redox capacity and increased the carrier density of CGMOF by 2.74-fold compared to that of MOF. In addition, cinnamaldehyde was grafted onto CGMOF for tumor-responsive hydrogen peroxide self-supply. Concurrently, hyaluronic acid was surface-modified to achieve the targeted delivery of nano-photosensitizers. In summary, this study presents an innovative approach for engineering Fe-based metal–organic frameworks for synergetic PDT/CDT applications.

Modifying Proton Relay into Bioinspired Dye-Based Coordination Polymer for Photocatalytic Proton-Coupled Electron Transfer.

Proton-coupled electron transfer (PCET) imparts an energetic advantage over single electron transfer in activating inert substances. Natural PCET enzyme catalysis generally requires tripartite preorganization of proton relay, substrate-bound active center, and redox mediator, making the processes efficient and precluding side reactions. Inspired by this, a heterogeneous photocatalytic PCET system was established to achieve higher PCET driving forces by modifying proton relays into anthraquinone-based anionic coordination polymers. The proximally separated proton relays and photoredox-mediating anthraquinone moiety allowed pre-assembly of inert substrate between them, merging proton and electron into unsaturated bonds by photoreductive PCET, which enhanced reaction kinetics compared with the counter catalyst without proton relay. This photocatalytic PCET method was applied to a broad-scoped reduction of aryl ketones, unsaturated carbonyls, and aromatic compounds. The distinctive regioselectivities for the reduction of isoquinoline derivatives were found to occur on the carbon-ring sides. PCET-generated radical intermediate of quinoline could be trapped by alkene for proton relay-assisted Minisci addition, forming the pharmaceutical aza-acenaphthene scaffold within one step. When using heteroatom(X)-H/C-H compounds as proton-electron donors, this protocol could activate these inert bonds through photooxidative PCET to afford radicals and trap them by electron-deficient unsaturated compounds, furnishing the direct X-H/C-H functionalization.

Boosted charge separation in porphyrin-based MOFs/CdS photocatalyst via interfacial −N−Cd− bridge bond construction

The high interfacial charge transfer barrier has been a main thermodynamic obstacle for improving the catalytic efficiency of heterojunction materials. Optimizing the interfacial environment is an effective strategy to achieve high catalytic efficiency. Herein, the coordinate bond (−N−Cd−) is designed to connect the hafnium porphyrin−metal organic framework (HT) and CdS nanoparticles, which is systematically analyzed by the 1H NMR, FTIR, Raman and DRS, respectively. The optimized 15HT1.5 H/CdS6 composite featuring interfacial bridge bonds, exhibits an H2 production up to 11.9 mmol·g−1·h−1, which is 28.5, 52.8 and 7 times greater than pure CdS, HTH, and mechanically mixed sample without interfacial chemical bonds connected, respectively. Mechanistic study suggests that the coordination bonds between HT and CdS serve as the directional carrier transfer bridges, significantly improving interfacial charge separation and chemical stability. Moreover, the formed Z-scheme charge transfer mechanism also endows the composite with high redox ability. This strategic construction of interfacial chemical bonds within heterojunction provides an effective pathway for improving interfacial charge transfer in the heterojunction photocatalysts.

A combined experimental and theoretical study on the mechanism of catalytic oxidation of lignite to carboxylic acids by iron

The oxygen-oxidation of lignite to carboxylic acids (CAs) using environmentally friendly iron catalyst represents an efficient and clean technology for lignite utilization. However, the mechanism remains unclear due to the difficulty in observing the cleavage of chemical bonds and the challenge in capturing transient intermediates and radicals. In this work, the microscopic reaction mechanism of iron-catalytic oxidation of lignite was investigated by combining experimental and theoretical methods. Catalytic oxidation experiments revealed that water-soluble intermediates generated by solid-state lignite decomposition underwent a continuous carbon–carbon bond cleavage oxidation (including oxidative cleavage of aliphatic moieties and oxidative ring-opening of aromatic moieties) to form CAs with aldehyde moieties as the direct precursor. Based on molecular dynamics simulations and density functional theory, a reaction network from lignite to CAs was proposed. The iron catalyst was present in the form of iron-aqua complexes in the liquid phase and iron-phenyl complexes in the solid phase. These iron-aqua/iron-phenyl complexes could reduce the energies of oxidation reactions, promoting the cleavage of bridge bonds, the formation of o-quinones and the oxidation of aromatic moieties, thus accelerating elementary reactions for the formation of CAs. These findings provide a theoretical support for the oxidation of lignite and an in-depth insight into iron-catalytic mechanism.

Thermal reactivity and gas–solid product evolution during coal catalytic combustion: An experimental study

To achieve efficient and clean coal combustion, catalytic combustion technology has received widespread attention. This paper systematically studied the influence of calcium-based compounds on the thermal reactivity and gas–solid two-phase product evolution behavior of different coal using TG-MS and FTIR analysis, combining kinetics and thermodynamics methods, the catalytic coal mechanism was discussed. Results demonstrated that both catalysts improved the combustion reactivity, the burnout temperatures of lignite, bituminous coal and anthracite were reduced by 30.75 °C, 53 °C and 25.5 °C respectively with CaO, as well as decreased by 24.75 °C, 55.5 °C and 29 °C respectively with CaCl2. Meanwhile, it was worth noting that the activation energy of three coals was also reduced. CaCl2 was more likely to bind with the C = O functional group on the surface of coal, forming CO-Ca2+ complexes, resulting in a decrease in the content of C = O and C-O. While CaO tended to absorb volatile matter, causing local overheating and promoting the breakage of side chains and bridge bonds. Besides, the calcium-based compounds advanced the gas evolution peak of combustion and the emissions of CO2, NO2 and SO2 were effectively controlled. These results aimed at providing a new reference direction for further industrial development of clean coal combustion technology.

Evolution and generation mechanism of retained oil in lacustrine shales: A combined ReaxFF-MD and pyrolysis simulation perspective

To accurately investigate the evolution characteristics and generation mechanism of retained oil, the study analyzed organic-rich lacustrine shale samples from the Paleogene Kongdian Formation in Cangdong Sag, Bohai Bay Basin. This analysis involves Rock-Eval pyrolysis, pyrolysis simulation experiments, Gas Chromatograph Mass Spectrometer (GC–MS), and reactive molecular dynamics simulations (ReaxFF). The results revealed the retained oil primarily consisted of n-alkanes with carbon numbers ranging from C14 to C36. The generation of retained oil occurred through three stages. A slow growth stage of production rate was observed before reaching the peak of oil production in Stage I. Stage II involved a rapid increase in oil retention, with C12–C17 and C24–C32 serving as the primary components, increasing continuously during the pyrolysis process. The generation process involved the cleavage of weak bonds, including bridging bonds (hydroxyl, oxy, peroxy, imino, amino, and nitro), ether bonds, and acid amides in the first stage (Ro =0.50%–0.75%). The carbon chains in aromatic ring structures with heteroatomic functional groups breaks in the second stage (Ro =0.75%–1.20%). In the third stage (Ro =1.20%–2.50%), the ring structures underwent ring-opening reactions to synthesize iso-short-chain olefins and radicals, while further breakdown of aliphatic chains occurred. By coupling pyrolysis simulation experiments and molecular simulation technology, the evolution characteristics and bond breaking mechanism of retained oil in three stages were revealed, providing a reference for the formation and evolution mechanism of retained oil.

A Site-Specific Cross-Linker for Visible-Light Control of Proteins.

There is a need for photochemical tools that allow precise control of protein structure and function with visible light. We focus here on the s-tetrazine moiety, which can be installed at a specific protein site via the reaction between dichlorotetrazine and two adjacent sulfhydryl groups. Tetrazine's compact size enables structural mimicry of native amino acid linkages, such as an intramolecular salt bridge or disulfide bond. In this study, we investigated tetrazine installation in three different proteins, where it was confirmed that the cross-linking reaction is highly efficient in aqueous conditions and site-specific when two cysteines are located proximally: the S-S distance was 4-10 Å. As shown in maltose binding protein, the tetrazine cross-linker can replace an interdomain salt bridge crucial for xenon binding and serve as a visible-light photoswitch to modulate 129Xe NMR contrast. This work highlights the ease of aqueous tetrazine bioconjugation and its applications for protein photoregulation.

A highly effective method for the environmentally friendly production of novel chromene derivatives using electron deficient compounds

AbstractNew, high‐yield derivatives of oxepino[3,2‐c]chromene were synthesized through a multicomponent reaction. This reaction involved 2‐hydroxyacetophenone, dimethyl carbonate, activated acetylenic compounds, and alkyl bromide. The reaction took place at room temperature in an aqueous environment, resulting in the formation of these innovative compounds. Oxathiepines were synthesized using multicomponent reactions of 2‐hydroxyacetophenone, dimethyl carbonate, isothiocyanate, and alkyl bromide in water at room temperature. This technology offers several benefits, including quick response times, high product yields, and easy product separation using straightforward techniques.

A sustainable rapeseed oil-based bio-additive designed for hard asphalt binders: Performance, environmental, and economic assessment

The inherent properties of hard asphalt binder give it both mechanical and economic benefits, rendering it a naturally advantageous material for preventing permanent deformation at higher temperatures. However, its poor resistance to thermal and fatigue cracking limits its application in the paving industry. This study aimed to improve the low-temperature and fatigue performance of hard asphalt binders by using the newly developed vegetable oil-based sub-epoxidized rapeseed oil (SERO). Two SEROs with epoxidation degree of 49.1% and 98.1% were synthesized through an oxidation reaction, respectively. Subsequently, the microstructural characteristics of SEROs were examined by Fourier transform infrared spectroscopy (FTIR) and Hydrogen nuclear magnetic resonance tests. The anti-oxidative aging properties of SERO modified hard asphalt binders were investigated through the utilization of mass loss and aging index. Additionally, the comprehensive rheological properties of SERO modified hard asphalt binders were explored via dynamic shear rheometer and bending beam rheometer tests. Furthermore, the modification mechanism of SERO on hard asphalt binders was confirmed through the quantitative analysis using the FTIR test. The findings suggested the improvement in anti-volatilization and anti-oxidative aging performance of bio-modified hard asphalt binders, which was positively related to the epoxidation degree of SERO. A notable softening effect of SERO on the hard asphalt binders was observed, which enhanced their resistance to thermal and fatigue cracking at lower and intermediate temperatures. The epoxy groups within SERO engaged in ring-opening reactions, forming a new oxygen bridge bond by combining with the unsaturated double bond presented in the asphalt. Consequently, this process resulted in the formation of cross-linked structures within bio-modified hard asphalt binders, thereby enhancing the elasticity. Notably, this phenomenon was most conspicuous in the SERO-H modified 50# binder. Finally, the environmental and economic assessment of SERO modified hard asphalt binders were conducted by the techno-economic method and the emission factors technique. The data revealed that the production of one ton of SERO modified hard asphalt binders could reduce the production costs by about 30%, energy consumption and CO2 emissions by around 20% in contrast to styrene–butadiene–styrene block copolymer modified asphalt binders. Hence, the substantial economic and environmental advantages make SERO an attractive bio-renewable additive for sustainable pavements.

Kinetic Isotope Effects and the Mechanism of CO2 Insertion into the Metal-Hydride Bond of fac-(bpy)Re(CO)3H.

The 1,2-insertion reaction of CO2 into metal-hydride bonds of d6-octahedral complexes to give κ1-O-metal-formate products is the key step in various CO2 reduction schemes and as a result has attracted extensive mechanistic investigations. For many octahedral catalysts, CO2 insertion follows an associative mechanism in which CO2 interacts directly with the coordinated hydride ligand instead of the more classical dissociative mechanism that opens an empty coordination site to bind the substrate to the metal prior to a hydride migration step. To better understand the associative mechanism, we conducted a systematic quantum chemical investigation on the reaction between CO2 and fac-(bpy)Re(CO)3H (1-Re-H; bpy = 2,2'-bipyridine) starting with the gas phase and then moving to THF and other solvents with increased dielectric constants. Detailed analyses of the potential energy surfaces (PESs) and intrinsic reaction coordinates (IRCs) reveal that the reaction is enabled in all media by an initial stage of making a 3c-2e bond between the carbon of CO2 and the metal-hydride bond that is most consistent with an organometallic bridging hydride Re-H-CO2 species. Once CO2 is bent and anchored to the metal-hydride bond, the reaction proceeds by a rotation motion via a cyclic transition state TS2 that interchanges Re-H-CO2 and Re-O-CHO coordination. The combined stages provide an asynchronous-concerted pathway for CO2 insertion on the Gibbs free energy surface with TS2 as the highest energy point. Consideration of TS2 as a rate-determining TS gives activation barriers, inverse KIEs, substituent effects, and solvent effects that agree with the experimental data available in this system. An important new insight revealed by the analyses of the results is that the initial stage of the reaction is not a hydride transfer step as has been assumed in some studies. In fact, the loose vibration of the TS that can be identified for the first stage of the reaction in solution (TS1) does not involve the Re-H stretching vibrational mode. Accordingly, the imaginary frequency of TS1 is insensitive to deuteration, and therefore, TS1 leads to no significant KIE.

Understanding the Electronic Structure and Chemical Bonding in the 2D Fullerene Monolayer.

Recently synthesized two-dimensional (2D) monolayer quasi-hexagonal-phase fullerene (qHPC60) demonstrates excellent thermodynamic stability. Within this monolayer, each fullerene cluster is surrounded by six adjacent C60 cages along an equatorial plane and is connected by both C-C single bonds and [2 + 2] cycloaddition bonds that serve as bridges. In this study, we investigate the stability mechanism of the 2D qHPC60 monolayer by examining the electronic structure and chemical bonding through state-of-the-art theoretical methodologies. Density functional theory (DFT) studies reveal that 2D qHPC60 possesses a moderate direct electronic band gap of 1.46 eV, close to the experimental value (1.6 eV). It is found that the intermolecular bridge bonds play a crucial role in enhancing the charge flow and redistribution among C60 cages, leading to the formation of dual π-aromaticity within the C60 sphere and stabilizing the 2D framework structure. Furthermore, we identify a series of delocalized superatom molecular orbitals (SAMOs) within the 2D qHPC60 monolayer, exhibiting atomic orbital-like behavior and hybridization to form nearly free-electron (NFE) bands with σ/π bonding and σ*/π* antibonding properties. Our findings provide insights into the design and potential applications of NFE bands derived from SAMOs in 2D qHPC60 monolayers.

Spectral Investigations of 60S Bioactive Glass Modified with La and Y Ions.

The changes in the atomic structure and in the network of bonds between oxide tetrahedra in 60S bioactive glass upon modification of its structure by yttrium and lanthanum atoms were investigated via XPS, FTIR, and NMR spectroscopy methods. The presence of nanostructure in the samples of 60S bioactive glass modified with yttrium and lanthanum was demonstrated. The formation of a bioinert core of 60S bioactive glass nanoparticles with the subsequent formation of a biocompatible layer is facilitated by the redistribution of electron density when oxygen bridge bonds are broken, PO4 and SiO4 tetrahedra are fragmented in the polymer matrix, and isolated nanoclusters are formed. Given the fact that during the interaction with the extracellular matrix, the breakdown of covalent bonds -O-Si-O-P- is more energetically costly than the rapid ionic exchange of network modifiers Ca2+ (Y3+, La3+) and the leaching of isolated nanoclusters into the surrounding physiological environment, it is argued that modification of 60S bioactive glass with yttrium or lanthanum can accelerate bioactive ionic processes in the extracellular matrix.

Investigation of the Biological Activity of Pyrrolo[1,2-a]imidazole Derivatives Produced by a Green One-Pot Multicomponent Synthesis of Ninhydrins

Aims & Objective: This study entailed the creation of a new variation of pyrroloimidazoles with exceptional efficacy through chemical synthesis. The synthesis was accomplished by tricomponent reactions utilizing ninhydrins, diamines, and activated acetylenic compounds in an aqueous setting, leading to significant yields. The antioxidant properties of recently synthesized Pyrroloimidazoles derivatives have been ascribed to the existence of NH and OH groups, which were evaluated using two techniques. The antimicrobial effectiveness of recently developed pyrroloimidazoles was evaluated using a disk diffusion technique against both Gram-negative and Gram-positive bacteria. Materials and Methods: The study team utilized high-quality starting chemicals, solvents, and reagents with consistent chemical and physical properties. The Shimadzu IR-460 spectrometer was used in a KBr medium to get the Ft-IR spectra of the synthesized nanocatalyst. Furthermore, we employed a Bruker DRX-400 AVANCE spectrometer to acquire 1H-NMR and 13C-NMR spectra of the synthesized compounds. The spectrometer utilized in this investigation functions at a frequency of 400 MHz. The solvent employed for the spectra of produced compounds was CDCl3, with TMS serving as the internal standard. The mass spectra of the produced compounds, which have an ionization potential of 70 eV, were obtained using the Finnigan MAT 8430 spectrometer. Elements of produced compounds were subjected to elemental analysis using the Heraeus CHN-O-Rapid analyzer. Results: This work investigated the three-component reaction involving ninhydrins 1, diamines 2, and electron-deficient acetylenic compounds 3 for the eco-friendly production of pyrroloimidazoles derivatives 4 in water-based solutions at normal temperature. The results indicated that these molecules displayed noteworthy efficacy, similar to that of conventional antioxidants. Also, the results indicated that the synthesized pyrroloimidazoles have bacteriostatic properties. Conclusion: In summary, this study aimed to examine the environmentally friendly characteristics of ninhydrins, diamines, and electron-deficient acetylenic compounds when dissolved in water at normal room temperature. The research resulted in the successful production of new pyrroloimidazole derivatives with a high rate of success. This study conducted a more in-depth analysis of the antioxidant properties of the synthesized pyrroloimidazoles 4a-4d by the utilization of two techniques: DPPH radical scavenging and FRAP assays. The results indicated that these molecules displayed noteworthy efficacy, similar to that of conventional antioxidants. Furthermore, we utilized both Gram-positive and Gram-negative bacteria to showcase the antibacterial effectiveness of the synthesized pyrroloimidazoles by the disk diffusion technique. The results indicated that the synthesized pyrroloimidazoles have bacteriostatic properties. These reactions provide benefits, such as efficient utilization of atoms, generation of large quantities of products, and straightforwardness of the reaction.

Valorization of lignite to arene-rich compounds via two-stage selective cleavage of C-O bridged bonds over Co-MoS2

Directly converting lignite into arenes as commodity chemicals and drop-in fuels is a highly desirable target for researchers. However, this is severely limited by the presence of stable inter unit C-O linkages in lignite. Herein, a highly active catalyst, Co-MoS2, has been designed and prepared to be used for the selective catalytic cleavage of inter unit C-O bridged bonds (BBs) in the conversion of Naomaohu (NMH), a lignite, to yield arenes. Both catalytic hydrogenation conversion (CHC) and thermal dissolution (a non-catalytic process, named NCHC) of NMH were conducted using n-hexane as the solvent. The soluble fractions from the first stage of NCHC (SFNCHC-1) and CHC (SFCHC-1), as well as the second stage of NCHC (SFNCHC-2) and CHC (SFCHC-2) were obtained using the same solvent. After the first-stage catalytic treatment, the relative contents of arenes and alkanes in SFCHC-1 increased by 16.7 % and 9.3 %, respectively, compared to those in SFNCHC-1, and the relative content of oxygen-containing compounds (OCCs), such as alcohols, phenols, esters, ketones, acids, and furans, decreased by 13.2 %. For the second-stage conversion, the relative contents of arenes and alkanes in SFCHC-2 were 53.5 % and 15.5 % higher than those in SFNCHC-2, and the relative contents of OCCs was only 6.6 % in SFCHC-2. The catalytic mechanisms of cleavage of C-O BBs and deoxygenation were proposed based on the CHC of model compounds and density functional theory (DFT) calculation. The adsorption of OCCs and the activation of released hydrogen radical (H·) by Co-MoS2, followed by H· addition to the carbon atom connected to oxygen in C-O BBs and oxygen-containing functional groups, are crucial for the cleavage of C-O BBs and formation of deoxygenated compounds, particularly arenes.

Bridge effect on charge transfer and energy transfer in fullerene-chromophore dyads.

Fullerene-chromophore dyads have attracted a great deal of research interest because these complexes can be potentially designed as nanoscale artificial photosynthetic centers, in which the chromophore and fullerene function as the electron donor and acceptor, respectively. The basic operation of this dyad-type artificial reaction center is photoinduced electron transfer from the donor to the acceptor. The fullerene and chromophore are usually covalently linked so that sufficient electronic coupling between these two moieties can facilitate the electron transfer. However, other deactivation pathways for the chromophore excited state, such as energy transfer to the fullerene, may reduce the quantum yield of the photoinduced electron transfer. Here, a series of C60-perylene dyads is exploited to interrogate the effect of the linkage on deactivation mechanisms of the chromophore excited state. For the C60-perylene dyads with a single or double bond bridge, we find that the decay of the singlet state of the chromophore is dominated by the electron transfer, and the corresponding time constant is determined to be 45ps. On the other hand, for the dyad with a triple bond bridge, the singlet state of the chromophore is quickly quenched through energy transfer to fullerene, and the time constant is as short as 7.9ps. Our finding suggests that the bond order of the bridge in the fullerene-chromophore dyads can be utilized to control the deactivation pathways of the excited state.

Atomistic Removal Mechanisms of SiC in Hydrogen Peroxide Solution.

To elucidate the atomic mechanisms of the chemical mechanical polishing (CMP) of silicon carbide (SiC), molecular dynamics simulations based on a reactive force field were used to study the sliding process of silica (SiO2) abrasive particles on SiC substrates in an aqueous H2O2 solution. During the CMP process, the formation of Si-O-Si interfacial bridge bonds and the insertion of O atoms at the surface can lead to the breakage of Si-C bonds and even the complete removal of SiC atoms. Furthermore, the removal of C atoms is more difficult than the removal of Si atoms. It is found that the removal of Si atoms largely influences the removal of C atoms. The removal of Si atoms can destroy the lattice structure of the substrate surface, leading the neighboring C atoms to be bumped or even completely removed. Our research shows that the material removal during SiC CMP is a comprehensive result of different atomic-level removal mechanisms, where the formation of Si-O-Si interfacial bridge bonds is widespread throughout the SiC polishing process. The Si-O-Si interfacial bridge bonds are the main removal mechanisms for SiC atoms. This study provides a new idea for improving the SiC removal process and studying the mechanism during CMP.

Simultaneous Emerging Contaminant Removal and H2O2 Generation Through Electron Transfer Carrier Effect of Bi─O─Ce Bond Bridge Without External Energy Consumption.

Conventional advanced oxidation processes (AOPs) require significant external energy consumption to eliminate emerging contaminants (ECs) with stable structures. Herein, a catalyst consisting of nanocube BiCeO particles (BCO-NCs) prepared by an impregnation-hydrothermal process is reported for the first time, which is used for removing ECs without light/electricity or any other external energy input in water and simultaneous in situ generation of H2O2. A series of characterizations and experiments reveal that dual reaction centers (DRC) which are similar to the valence band/conducting band structure are formed on the surface of BCO-NCs. Under natural conditions without any external energy consumption, the BCO-NCs self-purification system can remove more than 80% of ECs within 30min, and complete removal of ECs within 30min in the presence of abundant electron acceptors, the corresponding second-order kinetic constant is increased to 3.62 times. It is found that O2 can capture electrons from ECs through the Bi─O─Ce bond bridge during the reaction process, leading to the in situ production of H2O2. This work will be a key advance in reducing energy consumption for deep wastewater treatment and generating important chemical raw materials.

Hydrogen‐Bond‐Mediated Formation of C−N or C=N Bond during Photocatalytic Reductive Coupling Reaction over CdS Nanosheets

AbstractReductive amination of carbonyl compounds and nitro compounds represents a straightforward way to attain imines or secondary amines, but it is difficult to control the product selectivity. Herein, we report the selective formation of C−N or C=N bond readily manipulated through a solvent‐induced hydrogen bond bridge, facilitating the swift photocatalytic reductive coupling process. The reductive‐coupling of nitro compounds with carbonyl compounds using formic acid and sodium formate as the hydrogen donors over CdS nanosheets selectively generates imines with C=N bonds in acetonitrile solvent; while taking methanol as solvent, the C=N bonds are readily hydrogenated to the C−N bonds via hydrogen‐bonding activation. Experimental and theoretical study reveals that the building of the hydrogen‐bond bridge between the hydroxyl groups in methanol and the N atoms of the C=N motifs in imines facilitates the transfer of hydrogen atoms from CdS surface to the N atoms in imines upon illumination, resulting in the rapid hydrogenation of the C=N bonds to give rise to the secondary amines with C−N bonds. Our method provides a simple way to control product selectivity by altering the solvents in photocatalytic organic transformations.

Hydrogen-Bond-Mediated Formation of C-N or C=N Bond during Photocatalytic Reductive Coupling Reaction over CdS Nanosheets.

Reductive amination of carbonyl compounds and nitro compounds represents a straightforward way to attain imines or secondary amines, but it is difficult to control the product selectivity. Herein, we report the selective formation of C-N or C=N bond readily manipulated through a solvent-induced hydrogen bond bridge, facilitating the swift photocatalytic reductive coupling process. The reductive-coupling of nitro compounds with carbonyl compounds using formic acid and sodium formate as the hydrogen donors over CdS nanosheets selectively generates imines with C=N bonds in acetonitrile solvent; while taking methanol as solvent, the C=N bonds are readily hydrogenated to the C-N bonds via hydrogen-bonding activation. Experimental and theoretical study reveals that the building of the hydrogen-bond bridge between the hydroxyl groups in methanol and the N atoms of the C=N motifs in imines facilitates the transfer of hydrogen atoms from CdS surface to the N atoms in imines upon illumination, resulting in the rapid hydrogenation of the C=N bonds to give rise to the secondary amines with C-N bonds. Our method provides a simple way to control product selectivity by altering the solvents in photocatalytic organic transformations.