Reaction Of Precursor Research Articles

Pseudocyclic Arylbenziodoxaboroles as Water-Triggered Aryne Precursors in Reactions with Organic Sulfides.

Pseudocyclic arylbenziodoxaboroles are unique aryne precursors under neutral aqueous conditions that selectively react with organic sulfides, forming the corresponding sulfonium salts. This reaction is compatible with various substituents (alkyl, halogen, CN, NO2, CHO, and cyclopropyl) in the aromatic ring or alkyl group of the sulfide. Similar reactions of sulfoxides afford o-hydroxy-substituted sulfonium salts. The structures of key products were confirmed by X-ray analysis.

Design of new zwitterionic microparticles with intrinsic antibacterial activity

AbstractThe crosslinked porous microparticles based on glycidyl methacrylate, N‐vinylimidazole, and triethylene glycol dimethacrylate (molar ratio between monomers 40:30:30) obtained in the presence of three porogenic agents (toluene, n‐butyl acetate, and toluene:n‐butyl acetate mixture, 1:1, v/v) are used as precursors in the polymer analogous reactions with some betainizing agents (sodium monochloroacetate, acrylic acid, methacrylic acid and 1,3–propane sultone) in order to introduce the carboxybetaine/sulfobetaine groups to the tertiary nitrogen atom from the imidazole ring. ATR–FTIR spectroscopy is used to highlight the presence of carboxybetaine/sulfobetaine groups on the structure of the microparticles, but also to calculate the degree of betainization (55.91%–90.2%) The zwitterionic microparticles are characterized by scanning electron and atomic force microscopies, equilibrium swelling ratio as a function of pH values, swelling kinetics, ion exchange capacities and particle size distribution. Also, the parameters of porous structure (pore diameter, pore volume, porosity, and specific surface area) are determined by mercury porosimetry. The antibacterial properties of Gram‐positive (Enterococcus faecalis and Staphylococcus aureus) and Gram‐negative (Escherichia coli and Klebsiella pneumoniae) bacteria are evaluated. It is found that the zwitterionic structures containing a shorter length alkyl chain between ionic groups exhibit excellent antibacterial activity of about 80%–92%.

Photochemical oxidation of VOCs and their source impact assessment on ozone under de-weather conditions in Western Taiwan

The application of statistical models has excellent potential to provide crucial information for mitigating the challenging issue of ozone (O3) pollution by capturing its associations with explanatory variables, including reactive precursors (VOCs and NOX) and meteorology. Considering the large contribution of O3 in degrading the air quality of western Taiwan, three-year (2019–2021) hourly concentration data of VOC, NOX and O3 from 4 monitoring stations of western Taiwan: Tucheng (TC), Zhongming (ZM), Taixi (TX) and Xiaogang (XG), was evaluated to identify the effect of anthropogenic emissions on O3 formation. Owing to the high-ambient reactivity of VOCs on the underestimation of sources, photochemical oxidation was assessed to calculate the consumed VOC (VOCcons) which was followed by the source identification of their initial concentrations. VOCcons was observed to be highest in the summer season (16.7 and 22.7 ppbC) at north (TC and ZM) and in the autumn season (17.8 and 11.4 ppbC) in southward-located stations (TX and XG, respectively). Results showed that VOCs from solvents (25–27%) were the major source at northward stations whereas VOCs-industrial emissions (30%) dominated in south. Furthermore, machine learning (ML): eXtreme Gradient Boost (XGBoost) model based de-weather analysis identified that meteorological factors favor to reduce ambient O3 levels at TC, ZM and XG stations (−67%, −47% and −21%, respectively) but they have a major role in accumulating the O3 (+38%) at the TX station which is primarily transported from the upwind region of south-central Taiwan. Crucial insights using ML outputs showed that the finding of the study can be utilized for region-specific data-driven control of emission from VOCs-sources and prioritized to limit the O3-pollution at the study location-ns as well as their accumulation in distant regions.

Precursor design and cascade mechanism of RuO2·xH2O atomic layer deposition

As the unique nanofabrication technique, atomic layer deposition (ALD) can be used to deposit high-quality, uniform, and conformal nanoparticle coatings. Ru and its oxides (RuOx) are important materials in the fields of microelectronics and catalysis. In this work, the reaction of Ru precursors with different ligands on the hydroxylated surfaces were explored. The elimination of the pyrrolyl (Py) ligand is easier than that of the cyclopentadienyl (Py) ligand on the hydroxylated surface. The reaction involved in RuO2·xH2O ALD using RuPy2 and H2O as precursors was further investigated. During the RuPy2 reaction, the pyrrolyl ligand is eliminated by the substitution reaction with a surface hydroxyl group. However, the desorption of the pyrrole molecule is difficult due to the strong adsorption between the pyrrole molecule and Ru surface. During the H2O reaction, the H2O molecules further help the elimination of pyrrolyl ligands from the surface and the dissociative desorption of pyrrole molecules This unique reaction mechanism involved in the ALD of RuO2 with the assistance of H2O can be termed new cascade mechanism. These findings provide theoretical guidance for precursor design and ALD growth of metal oxides.

Hydrothermally synthetized WO3 coated stainless steel mesh for oil–water separation purposes

To separate oil–water mixtures especially in oil field operations, new energy-efficient methods are urgently required. Conventional separation techniques using demulsifiers for separation of oil–water mixtures or even use of membranes usually suffered from high cost and energy consumption, composition dependency of demulsifiers and fouling or inability of a single membrane to separate all types of oil–water mixtures. This research aimed to synthesize tungsten oxide-coated stainless steel mesh using the hydrothermal method, with a focus on evaluating its effectiveness in oil–water separation. The coating procedure was carried out using hydrothermal techniques, with an emphasis on investigating the impact of precursor concentration, pH levels, reaction temperature and duration, on the separation efficiency of the optimal coating solution. The hydrothermally coated stainless steel mesh was created within a polytetrafluoroethylene reaction vessel, submerged in a 150 ml aqueous solution containing 0.0094 mol of sodium tungstate di-hydrate at pH 3.0, achieved through the addition of hydrochloric acid. Additionally, 1 g of oxalic acid, acting as a chelating agent, was introduced. Subsequently, the mesh underwent a 4 h reaction at 220 °C and was subsequently annealed for 30 min in a 350 °C furnace. Remarkably, the resultant mesh exhibited an exceptional water separation flux of 9870 ± 15 L/hr/m2 when exposed to 1:1 v/v oil–water mixtures. This performance significantly outperformed previous filters designed for similar oil–water separation tasks. The mesh efficiently facilitated the passage of water through the oil–water mixture, achieving an efficiency rate exceeding 98 ± 1%. To gauge its wetting behavior, the hydrophilic/underwater oleophobic filter underwent static contact angle measurements. The filter's wetting mechanism was primarily attributed to its hierarchical surface structure, which enhanced surface hydrophilicity and roughness. Analytical techniques such as XRD, FTIR, and FE-SEM were employed to scrutinize the fabricated filter's composition. These analyses confirmed the successful creation of a nanostructured WO3 coating on both sides of the stainless steel mesh. Moreover, the utilization of commercially available chemicals and straightforward fabrication techniques underscores the promising potential of this approach for large-scale applications.

Synthesizing high performance LNMO cathode materials with porous structure by manipulating reynolds number in a microreactor

The demand for Lithium-ion batteries (LIBs) has significantly grown in the last decade due to their extensive use electric vehicles. To further advance the commercialization of LIBs for various applications, there is a pressing need to develop electrode materials with enhanced performance. The porous microsphere morphology LiNi x Mn2–x O4 (LNMO) is considered to be an effective material with both high energy density and excellent rate performance. Nevertheless, LNMO synthesis technology still has problem such as long reaction time, high energy consumption and environmental pollution. Herein, LNMO microsphere was successfully synthesized with short precursors reaction time (18 s) at 40 °C without using chelating agent by microreaction technology combined solid-state lithiation. The optimized LNMO cathode shows microsphere (∼8 μm) morphology stacked by nano primary particles, with abundant mesoporous and fully exposed low-energy plane. The electrochemical analysis indicates that the optimized LNMO cathode demonstrates 97.33% capacity retention even after 200 cycles at 1C. Additionally, the material shows a highly satisfactory discharge capacity of 92.3 mAh·g−1 at 10C. Overall, microreaction technology is anticipated to offer a novel approach in the synthesis of LNMO cathode materials with excellent performance.

Dietary intake of dicarbonyl compounds and changes in body weight over time in a large cohort of European adults.

Dicarbonyl compounds are highly reactive precursors of advanced glycation end products (AGE), produced endogenously, present in certain foods and formed during food processing. AGE contribute to the development of adverse metabolic outcomes, but health effects of dietary dicarbonyls are largely unexplored. We investigated associations between three dietary dicarbonyl compounds, methylglyoxal (MGO), glyoxal (GO) and 3-deoxyglucosone (3-DG), and body weight changes in European adults. Dicarbonyl intakes were estimated using food composition database from 263095 European Prospective Investigation into Cancer and Nutrition-Physical Activity, Nutrition, Alcohol, Cessation of Smoking, Eating Out of Home in Relation to Anthropometry participants with two body weight assessments (median follow-up time = 5·4 years). Associations between dicarbonyls and 5-year body-weight changes were estimated using mixed linear regression models. Stratified analyses by sex, age and baseline BMI were performed. Risk of becoming overweight/obese was assessed using multivariable-adjusted logistic regression. MGO intake was associated with 5-year body-weight gain of 0·089 kg (per 1-sd increase, 95 % CI 0·072, 0·107). 3-DG was inversely associated with body-weight change (-0·076 kg, -0·094, -0·058). No significant association was observed for GO (0·018 kg, -0·002, 0·037). In stratified analyses, GO was associated with body-weight gain among women and older participants (above median of 52·4 years). MGO was associated with higher body-weight gain among older participants. 3-DG was inversely associated with body-weight gain among younger and normal-weight participants. MGO was associated with a higher risk of becoming overweight/obese, while inverse associations were observed for 3-DG. No associations were observed for GO with overweight/obesity. Dietary dicarbonyls are inconsistently associated with body weight change among European adults. Further research is needed to clarify the role of these food components in overweight and obesity, their underlying mechanisms and potential public health implications.

Molecular dyad exhibiting strong multi‐resonance blue fluorescence

AbstractA multi‐resonance (MR) fluorophore exhibiting circularly polarized luminescence (CPL) holds a significant promise for enhancing the utility of organic light‐emitting devices. To meet this demand, we have devised molecular dyads having azaoxaborin MR emitters based on homochiral (R)‐ and (S)‐1,1′‐bi‐2‐naphthol. The synthesized 12,12′‐di‐tert‐butyl‐9,9′‐bi(8,8′‐dioxa‐4b,4′b‐diaza‐14b,14′b‐diborafluorantheno[1,2,3‐de]tetracene) products (TBNBOCz) exhibit strong blue fluorescence, with a remarkable 100% fluorescence quantum yield and an extremely narrow full width at half‐maximum of 22 nm. However, unexpectedly, TBNBOCz exhibits negligible electric circular dichroism and CPL activities. Chiroptical investigations into the reaction precursors reveals an occurrence of racemization in the borylation step. This result emphasizes the importance of understanding synthetic processes and their impact on the chiroptical properties.

Synthesis and Photocatalytic Activity of High-Quality Lead(II) Sulfide Nanoparticles from Lead(II) Thiosemicarbazone Complexes as Single Source Precursors

We report the synthesis of lead(II) complexes of 2-(thiophen-2-ylmethylene) hydrazine-1-carbothioamide (1) and 2-(1-(thiophen-2-yl) ethylene) hydrazine-1-carbothioamide (2), which were used as single source precursors in hexadecylamine (HDA) and oleylamine (OLA) at 190, 230, and 270°C to synthesize lead(II) sulfide nanoparticles. Optical studies by UV–vis analysis showed a general blue shift in the absorption band edge of the PbS nanoparticles (NPs) with energy bandgaps determined by Tauc’s plots ranging from 2.15 to 3.11 eV. The development of NPs with a variety of morphologies that changed with temperature and precursor type was demonstrated by morphological characterization using scanning electron microscopy and transmission electron microscopy. Cubic, rod-shaped, and nearly spherical-shaped PbS were formed. Powder X-ray diffraction (p-XRD) structural studies revealed the face-centered cubic structure of PbS nanoparticles. The elements contained in the nanoparticles were identified by energy dispersive X-ray spectroscopy (EDX). These results suggest that the size, shape, and optical properties of the synthesized PbS NPs were affected by reaction temperature, capping group, and precursor type. Under UV irradiation, the photocatalytic activity of HDA-capped PbS nanoparticles on the degradation of methylene blue dye ranged from 28.3% to 60.0%, with lead sulfide nanoparticle obtained by thermolysis of complex (1) at 230°C showing the highest photocatalytic efficiency (60.0%).

Finely Tuning Metal Ion Valences of [Fe3-xMx(μ3-OH)(Carboxyl)6(pyridyl)2] Cluster-Based ant-MOFs for Highly Improved CO2 Capture Performances.

Solvothermal reactions of different trinuclear precursors and 5-(pyridin-4-yl)isophthalic acid (H2L) successfully led to four anionic ant topological MOFs as Fe3-xMx(μ3-OH)(CH3COO)2(L)2·(DMA+)·DMF [M = Mn(II), Fe(II), Co(II), x = 0, 1, 2 and 3], namely, NJTU-Bai79 [NJTU-Bai = Nanjing Tech University Bai's group, Mn3(μ3-OH)], NJTU-Bai80 [Fe2Mn(μ3-OH)], NJTU-Bai81 [Fe3(μ3-OH)], and NJTU-Bai82 [Fe2Co(μ3-OH)], which possess the narrow pores (2.5-6.0 Å). NJTU-Bai80-82 is able to be tuned to the neutral derivatives [NJTU-Bai80-82(-ox), ox = oxidized] with M2+ ions oxidized to M3+ ones in the air and the OH- ions coordinated on M3+ ions. Very interestingly, selective CO2/N2 adsorptions of NJTU-Bai80-82(-ox) are significantly enhanced with the CO2 adsorption uptakes more than about 6 times that of NJTU-Bai79. GCMC simulations further revealed that neutral NJTU-Bai80-82(-ox) supplies more open frameworks around the -CH3 groups at separate spaces to the CO2 gas molecules with relatively more pores available to them after the removal of counterions. For the first time, finely tuning metal ion valences of metal clusters of ionic MOFs and making them from electrostatic to neutral were adopted for greatly improving their CO2 capture properties, and it would provide another promising strategy for the exploration of high-performance CO2 capture materials.

Over 10% Efficient Sb2(S,Se)3 Solar Cells Enabled by CsI-Doping Strategy.

Antimony selenosulfide (Sb2(S,Se)3) is an emerging quasi-1D photovoltaic semiconductor with exceptional photoelectric properties. The low-symmetry chain structure contains complex defects and makes it difficult to improve electrical properties via doping method. This article reports a doping strategy to enhance the efficiency of Sb2(S,Se)3 solar cells by using alkali halide (CsI) as the hydrothermal reaction precursor. It is found that the Cs and I ions are effectively doped and atomically coordinate with Sb ions and S/Se ions. The CsI-doping Sb2(S,Se)3 absorbers exhibit enhanced grain morphologies and reduced trap densities. The consequential CsI-doping Sb2(S,Se)3 based solar cells demonstrate favorable band alignment, suppressed carrier recombination, and improved device performance. An efficiency as high as 10.05% under standard AM1.5 illumination irradiance is achieved. This precursor-based alkali halide doping strategy provides a useful guidance for high-efficiency antimony selenosulfide solar cells.

Anion‐Stabilized Precursor Inks Toward Efficient and Reproducible Air‐Processed Perovskite Solar Cells

AbstractDespite the outperforming power conversion efficiency of low‐temperature and solution‐processed perovskite solar cells (PSCs) realized over the past decades, the undesirable stability from precursor inks to resultant devices and harsh preparation requirements still restrain their industrial production and practical deployment. Herein, an anion stabilization strategy is developed to achieve the comprehensive durability of perovskite photovoltaics throughout the whole two‐step air‐processed procedure. The effect of interionic bonding strengths on the ink properties, film crystallization, and photovoltaic performances is in‐depth explored and revealed. The pseudohalide bis(trifluoromethanesulfonyl)imide ions (TFSI−) not only improve the dispersion and stabilities of lead polyhalides and organic salt inks via strong electron‐withdrawing/donating chemical sites, but also realize high composition uniformity and preferential crystal growth of subsequent deposited perovskite layers by tuning the precursor reactivity and surface absorption. Ultimately, the optimizing PSCs deliver a superior efficiency of 24.16%, accompanied by notably improved long‐term stability toward extreme environmental and mechanical stimuli with lead leakage suppression. This work opens up a promising avenue toward reproducible air preparation of highly efficient, stable, and environmentally friendly perovskite optoelectronic devices via precise modulation of precursor properties.

Encapsulation of Er-doped GeO2 nanofilms by Al2O3 atomic layers: Surficial sensitivity to trimethylaluminum and improvement on electroluminescence

Based on previous results of the Er-doped GeO2 nanofilms fabricated by atomic layer deposition (ALD), the interfacial reactions of Al2O3 precursor within the GeO2/Al2O3:Er nanolaminates are investigated. The ALD pulse of Al(CH3)3 etches the as-deposited GeO2 nanofilm, while the oxidation of Al(CH3)3 by ozone realizes the deposition of atomic Al2O3 layer onto GeO2 surface. The Al2O3 atomic layers with ≥4 ALD cycles improve the thermal stability of the ALD GeO2 nanofilms, which restrain the formation of nanograins and also the reduction of film thickness during high-temperature annealing, giving rise to smooth GeO2/Al2O3:Er nanolaminates. For the 1530 nm electroluminescence (EL) from the silicon-based devices fabricated using the GeO2/Al2O3:Er nanolaminates annealed at 800 °C, the excitation efficiency is tripled to 22.1 %. The conduction of the energetic electrons resulting in the EL emissions still confirms to the trap-assisted tunneling mechanism within these amorphous GeO2/Al2O3:Er nanolaminates. The prototype devices based on the Al2O3-inserted nanolaminates exhibit comparatively increased operation time. These GeO2/Al2O3:Er nanolaminates with enhanced stability and improved optoelectronics performance pave the way for the practical utilization of ALD GeO2 nanofilms.

Preparation of Surface Dispersed WO3/BiVO4 Heterojunction Arrays and Their Photoelectrochemical Performance for Water Splitting.

In this work, a surface dispersed heterojunction of BiVO4-nanoparticle@WO3-nanoflake was successfully prepared by hydrothermal combined with solvothermal method. We optimized the morphology of the WO3 nanoflakes and BiVO4 nanoparticles by controlling the synthesis conditions to get the uniform BiVO4 loaded on the surface of WO3 arrays. The phase composition and morphology evolution with different reaction precursors were investigated in detail. When used as photoanodes, the WO3/BiVO4 composite exhibits superior activity with photocurrent at 3.53 mA cm-2 for photoelectrochemical (PEC) water oxidation, which is twice that of pure WO3 photoanode. The superior surface dispersion structure of the BiVO4-nanoparticle@WO3-nanoflake heterojunction ensures a large effective heterojunction area and relieves the interfacial hole accumulation at the same time, which contributes to the improved photocurrents together with the stability of the WO3/BiVO4 photoanodes.

Coherent X-ray Spectroscopy Elucidates Nanoscale Dynamics of Plasma-Enhanced Thin-Film Growth.

Sophisticated thin film growth techniques increasingly rely on the addition of a plasma component to open or widen a processing window, particularly at low temperatures. Taking advantage of continued increases in accelerator-based X-ray source brilliance, this real-time study uses X-ray Photon Correlation Spectroscopy (XPCS) to elucidate the nanoscale surface dynamics during Plasma-Enhanced Atomic Layer Deposition (PE-ALD) of an epitaxial indium nitride film. Ultrathin films are synthesized from repeated cycles of alternating self-limited surface reactions induced by temporally separated pulses of the material precursor and plasma reactant, allowing the influence of each on the evolving morphology to be examined. During the heteroepitaxial 3D growth examined here, sudden changes in the surface structure during initial film growth, consistent with numerous overlapping stress-relief events, are observed. When the film becomes continuous, the nanoscale surface morphology abruptly becomes long-lived with a correlation time spanning the period of the experiment. Throughout the growth experiment, there is a consistent repeating pattern of correlations associated with the cyclic growth process, which is modeled as transitions between different surface states. The plasma exposure does not simply freeze in a structure that is then built upon in subsequent cycles, but rather, there is considerable surface evolution during all phases of the growth cycle.

Early mechanical strength, hydration mechanism and leaching behavior of alkali-activated slag/fly ash paste filling materials

The enhancement of the early strength of the filling body is regarded as a critical technology for shortening the mining & filling cycle and achieving efficient production. It is a high-value utilization pathway to entirely replace Ordinary Portland Cement (OPC) with industrial waste residue. Hence, in this research, ground granulated blast furnace slag (GGBFS) and fly ash (FA) were selected as aluminosilicate precursors. The effects of single-component and binary activation of Na2SiO3, Na2SO4, Na2CO3, NaOH, NaAlO2 and triethanolamine (TEA) on the mechanical strength of backfill were systematically investigated. The microstructural evolution mechanism of hydration products was elucidated using XRD, TG-DTG, SEM and MIP analyses. The leaching characteristics and immobilization mechanism of heavy metals were further revealed. The experimental results indicated that the activator contributed an alkaline environment and active ions to the initial hydrolysis reaction of precursors and the polycondensation reaction of silica tetrahedra and aluminum tetrahedra with Ca2+ drove the hardening and development of the hydration products. Na2SiO3 exhibited the superior activation effect among single-component activators, while the binary activator presented notable “promoting and inhibiting characteristics”. Moreover, the binary activator composed of 4% Na2SiO3 and 4% NaAlO2 conducted the highest compressive strength at 3 d and 7 d. The dominant hydration products of the backfill were ettringite, C-S-H gels, C-A-S-H gels and zeolite-like products. The density of microstructures and the crystallinity of hydration products were significantly enhanced ascribed to the synergistic and complementary effects of Na2SiO3 and NaAlO2. Heavy metals were immobilized by the hydration products through physical encapsulation and chemical bonding, and the leaching concentrations of all heavy metals (Pb, Cd, Cr(Ⅵ), Zn, Mn, As and Cu, etc.) were lower than the standard limits of Class III in GB/T 14848-2017.

Friedel–Crafts Acylation for Accessing Multi‐Bridge‐Functionalized Large Pillar[n]arenes

AbstractPillar[n]arenes can be constructed using a Friedel–Crafts alkylation process. However, due to the reversible nature of the alkylation, mixture of large pillar[n]arenes (n≥7) are obtained as minor products, and thus laborious purification are necessary to isolate the larger pillar[n]arenes. Moreover, inert methylene bridges are introduced during the alkylation process, and the multi‐functionalization of the bridges has never been investigated. Herein, an irreversible Friedel–Crafts acylation is used to prepare pillar[n]arenes. Due to the irreversible nature of the acylation, the reaction of precursors bearing carboxylic acids and electron‐rich arene rings results in a size‐exclusive formation of pillar[n]arenes, in which the ring‐size is determined by the precursor length. Because of this size‐selective formation, laborious separation of undesired macrocycles is not necessary. Moreover, the bridges of pillar[n]arenes are selectively installed with reactive carbonyl groups using the acylation method, whose positions are determined by the precursor used. The carbonyl bridges can be easily converted into versatile functional groups, leading to various laterally modified pillar[n]arenes, which cannot be accessed by the alkylation strategy.

Friedel-Crafts Acylation for Accessing Multi-Bridge-Functionalized Large Pillar[n]arenes.

Pillar[n]arenes can be constructed using a Friedel-Crafts alkylation process. However, due to the reversible nature of the alkylation, mixture of large pillar[n]arenes (n≥7) are obtained as minor products, and thus laborious purification are necessary to isolate the larger pillar[n]arenes. Moreover, inert methylene bridges are introduced during the alkylation process, and the multi-functionalization of the bridges has never been investigated. Herein, an irreversible Friedel-Crafts acylation is used to prepare pillar[n]arenes. Due to the irreversible nature of the acylation, the reaction of precursors bearing carboxylic acids and electron-rich arene rings results in a size-exclusive formation of pillar[n]arenes, in which the ring-size is determined by the precursor length. Because of this size-selective formation, laborious separation of undesired macrocycles is not necessary. Moreover, the bridges of pillar[n]arenes are selectively installed with reactive carbonyl groups using the acylation method, whose positions are determined by the precursor used. The carbonyl bridges can be easily converted into versatile functional groups, leading to various laterally modified pillar[n]arenes, which cannot be accessed by the alkylation strategy.

Pd-incorporated polyoxometalate catalysts for electrochemical CO2 reduction.

Polyoxometalates (POMs), representing anionic metal-oxo clusters, display diverse properties depending on their structures, constituent elements, and countercations. These characteristics position them as promising catalysts or catalyst precursors for electrochemical carbon dioxide reduction reaction (CO2RR). This study synthesized various salts-TBA+ (tetra-n-butylammonium), Cs+, Sr2+, and Ba2+-of a dipalladium-incorporated POM (Pd2, [γ-H2SiW10O36Pd2(OAc)2]4-) immobilized on a carbon support (Pd2/C). The synthesized catalysts-TBAPd2/C, CsPd2/C, SrPd2/C, and BaPd2/C-were deposited on a gas-diffusion carbon electrode, and the CO2RR performance was subsequently evaluated using a gas-diffusion flow electrolysis cell. Among the catalysts tested, BaPd2/C exhibited high selectivity toward carbon monoxide (CO) production (ca. 90%), while TBAPd2/C produced CO and hydrogen (H2) with moderate selectivity (ca. 40% for CO and ca. 60% for H2). Moreover, BaPd2/C exhibited high selectivity toward CO production over 12 h, while palladium acetate, a precursor of Pd2, showed a significant decline in CO selectivity during the CO2RR. Although both BaPd2/C and TBAPd2/C transformed into Pd nanoparticles and WO x nanospecies during the CO2RR, the influence of countercations on their product selectivity was significant. These results highlight that POMs and their countercations can effectively modulate the catalytic performance of POM-based electrocatalysts in CO2RR.

On-surface polymerization reactions of dibrominated hexaphenylbenzene influenced by densely packed self-assembly.

Controlled bottom-up fabrication of molecular nanostructures through on-surface reactions of tailor-made precursors is of scientific and technological interest. Recently, on-surface polymerization reactions influenced by precursor self-assembly have been reported. Thus, a fundamental understanding of the reaction process is a prerequisite for controlled formation. Herein, we report on the influence of molecular self-assembly of dibrominated hexaphenylbenzene (Br2-HPB) on the on-surface polymerization reactions on a Au(111) substrate. By using low-temperature scanning tunnelling microscopy (STM), we find that the polymerization of Br2-HPB proceeds while maintaining the long-range ordered self-assembly, despite a decrease in HPB-HPB distance due to debromination and successive covalent bonding of Br2-HPB. From the STM investigations of the polymerization process, we conclude that the polymerization of Br2-HPB is accompanied by molecular rotations to maintain the periodic array of the self-assembled structure, contrary to the conventional understanding of the polymerization of the self-assembled precursor layer.