Yield Of Benzaldehyde Research Articles

Efficient cleavage of C-C bond in lignin adopting Z-scheme heterojunction photocatalyst by g-C3N4/CQDs/WO3

It is a practical approach to overcome the shortage of energy and environmental pollution simultaneously if obtaining useful products from biomass through chemical decomposition. Photocatalytic depolymerization of lignin to generate high value-added chemicals has received extensive attention for decades. The low yield of aromatic monomers is still one of the urgent problems to be solved. Selective breakage of Cα-Cβ bonds in lignin is of importance to improve the yield of aromatic monomers. Herein, Z-scheme heterojunction g-C3N4/CQDs/WO3 was constructed by combining graphite-like carbon nitride (g-C3N4), tungsten oxide (WO3) with carbon quantum dots (CQDs) to break the C-C bond selectively in β-O-4 model compounds. Both the efficiencies of substrate conversion and selectivity of C-C bond cleavage reached to 99 %. As a result, the total yield of benzaldehyde and benzoic acid attained to 83.92 %. Furthermore, the photocatalyst has satisfactory effect on depolymerization of four types of lignin, while the heterojunction can validly reduce the recombination rate of photogenerated carriers. Additionally, CQDs broadens the light absorption range and enhances the mobility of photogenerated carriers. Consequently, this study provides a feasible idea for highly selective cleavage of lignin C-C bonds through heterojunction engineering.

Efficient electrocatalytic [rad]OOH production on P–N–CuO for selective cleavage of lignin C–C bonds in the photoelectric collaborative system

Due to the mutual quenching of oxidizing groups and reducing groups, the yield of photocatalytic lignin cracking is not satisfactory. In this work, the oxidizing and reducing groups were separated in space by the method of photoelectric collaborative for the first time. The conversion rate of 2-phenoxy-1-phenylethanol (pp-ol) could be increased by 129.00 % and 31.47 % and the yield of benzoic acid and benzaldehyde increased by up to 19.56 % and 119.95 % in the photoelectric collaborative system compared with individual electrocatalysis and photocatalysis. P-doped N–CuO was used as electrocatalyst for directional and controllable generation of OOH free radicals, while g-C3N4 was used as photocatalyst to produce Cβ free radicals. For the mechanism, a new path of OOH and Cβ combining to fracture pp-ol was opened up. This work provides a new method to cracking lignin and used for aromatics production from renewable biomass feedstocks.

The Synthesis, Structural Characterization, and DFT Calculation of a New Binuclear Gd(III) Complex with 4-Aacetylphenoxyacetic Acid and 1,10-Phenanthroline Ligands and Its Roles in Catalytic Activity.

A new binuclear Gd(III) complex, [Gd2(L)6(Phen)2]·4H2O, was synthesized via the reaction of gadolinium(III) nitrate hexahydrate, 4-acetylphenoxyacetic acid (HL), NaOH, and 1,10-phenanthroline (Phen) in a solution of water-ethanol (v:v = 1:1). The Gd(III) complex was characterized using IR, UV-vis, TG-DSC, fluorescence, and single-crystal X-ray diffraction analyses. The results showed that the Gd(III) complex crystallizes in the triclinic system, space group P-1, and each Gd(III) ion was coordinated with two nitrogen atoms (N1, N2, or N1a, and N2a) from two Phen ligands and seven oxygen atoms (O1, O2, O7a, O9, O8, O8a, O10a, or O1a, O2a, O7, O8, O8a, O9a, and O10) from six L ligands, respectively, forming a nine-coordinated coordination mode. The Gd(III) complex molecules formed a one-dimensional chained and three-dimensional network structure via benzenering π-π stacking. The Hirschfeld surface analysis and the calculations of the electron density distributions of the frontier molecular orbitals of the Gd(III) complex were performed. The catalytic activities of the photocatalytic CO2 reduction and benzyl alcohol oxidation using the Gd(III) complex as a catalyst were performed. The results of the photocatalytic CO2 reduction showed that the yield and the selectivity of CO reached 41.5 μmol/g and more than 99% after four hours, respectively. The results of the benzyl alcohol oxidation showed that the yield of benzaldehyde was 45.7% at 120 °C with THF as the solvent under 0.5 MPa O2 within 2 h.

Synergistic coupling of photocatalytic H2 evolution and selective oxidation of benzyl alcohol over ZnIn2S4/Ni in aqueous solution

The synergistic coupling of photocatalytic hydrogen evolution and selective organic matter conversion is extremely attractive, as clean fuel and high value–added chemicals can be produced simultaneously with light as the sole energy input. Herein, we developed a dual functional photocatalyst (ZnIn2S4/Ni) for efficient photocatalytic conversion of benzyl alcohol into benzaldehyde with simultaneous hydrogen production. Consequently, ZnIn2S4/Ni displayed a top-level benzaldehyde and H2 evolution rate even in aqueous media. The yield of benzaldehyde reaches 19.3 mmol/g/h, which is 33 times higher than that of naked ZnIn2S4 and even exceeds that of precious metal systems (Pt, Pd, Ru). Here, Ni site not only acted as an effective co–catalyst for charge separation, but also played an important role in accelerating the α–C–H bond cleavage during the dehydrogenation of benzyl alcohol. This work provides a cost-effective and green reference path for the efficient conversion of solar energy to chemical energy.

Dually functional NiSi intermetallic compounds for the efficient hydrogenation and oxidation of cinnamaldehyde

Intermetallic compounds (IMCs) are promising catalysts for upgrading biomass-derived platform chemicals. Herein, bifunctional NiSi IMCs catalysts were developed for the hydrogenation and oxidation of cinnamaldehyde (CAL). A solvent-free arc-melting method was employed for the synthesis of NiSi IMCs within 5 min. The NiSi IMCs catalysts afforded 99 % conversion of CAL and presented ∼ 71 % yield of 2-phenyl propanol and ∼ 34 % yield of benzaldehyde for the hydrogenation and base-free oxidation of CAL, respectively. Moreover, NiSi IMCs could be used for five runs without deactivation. Characterizations and theoretical calculation results indicated the formation of intermetallic structure and the existence of Si vacancy sites, which could not only facilitate the efficient hydrogenation of CAL but also expose NiOx species as catalytic centers for the oxidation of CAL, leading to the high performance and stability in both hydrogenation and oxidation process.

Single-crystal oxygen-rich bismuth oxybromide nanosheets with highly exposed defective {10–1} facets for the selective oxidation of toluene under blue LED irradiation

Reactive radicals are crucial for activating inert and low-polarity C(sp3)-H bonds for the fabrication of high value-added products. Herein, novel single-crystal oxygen-rich bismuth oxybromide nanosheets (Bi4O5Br2 SCNs) with more than 85 % {10–1} facets exposure and oxygen defects were synthesized via a facile solvothermal route. The Bi4O5Br2 SCNs demonstrated excellent photocatalytic performance in the selective oxidation of toluene under blue light. The yield of benzaldehyde was 1876.66 μmol g−1 h−1, with a selectivity of approximately 90 %. Compared to that of polycrystalline Bi4O5Br2 nanosheets (Bi4O5Br2 PCNs), the activity of Bi4O5Br2 SCNs exhibit a 21-fold increase. Experimental studies and density functional theory (DFT) calculations have demonstrated that the defect Bi4O5Br2 (10–1) facets exhibits exceptional adsorption properties for O2 molecules. In addition, the single-crystal structure in the presence of surface defects significantly increases the separation and transport of photogenerated carriers, resulting in the effective activation of adsorbed O2 into superoxide radicals (•O2–). Subsequently, the positively charged phenylmethyl H is readily linked to the negatively charged superoxide radical anion, thereby activating the CH bond. This study offers a fresh perspective and valuable insights into the development of efficient molecular oxygen-activated photocatalysts and their application in the selective catalytic conversion of aromatic C(sp3)-H bonds.

Immobilized transition metal (II) bis–imine chelate on ZnO@TiO2 nanoparticles as sufficient catalysts for alcohol oxidation and for α,β‐cinnamic acid decarboxylative bromination

Based on the strong coordination ability of substituted imines towards transition metals of different oxidation states, the coordination of the HL imine ligand with the Cu2+ ion to form the Cu–bis–imine complex was achieved in 2:1 molar ratios. Their structures were confirmed with various spectroscopic tools. Heterogeneously, CuL2 was successfully appended on ZnO@TiO2 nanoparticles, as the less harmful materials, within the deprotonated p‐hydroxy chain of the bonded ligand in CuL2. The surface and internal structural morphologies of ZnO@TiO2@CuL2 were analyzed using X‐ray diffraction (XRD), field‐emission scanning electron microscopy (FESEM), high‐resolution transmission electron microscopy (HRTEM), energy‐dispersive X‐ray spectroscopy (EDS), and infrared (IR) spectroscopy, in addition to thermogravimetric analysis (TGA). The catalytic behavior of both catalysts, CuL2 (the homogeneous catalyst) and ZnO@TiO2@CuL2 (the heterogeneous catalyst), was examined in the benzyl alcohol redox protocols using H2O2 for their optimization. α,β‐Cinnamic acid decarboxylative bromination in the presence of potassium bromide and H2O2 in water was studied with both catalysts, in which (2‐bromovinyl)benzene was the chemoselective product. Both Cu catalysts displayed appreciable catalytic effectiveness for the oxidation protocols and the decarboxylative bromination reactions. CuL2 recorded less required time for optimization than that of the heterogeneous catalyst. The catalytic effectiveness of CuL2 was less promoted than that of ZnO@TiO2@CuL2. Despite the less performance in yield of benzaldehyde for the oxidation protocols with ZnO@TiO2@CuL2, ZnO@TiO2@CuL2 had more recycling than its homogeneous counterpart, with seven to three times, respectively.

Controllable introducing C, N-defects and oxygen-doping on carbon nitride to tune electronic structure and boost photocatalytic hydrogen evolution

In this work, one-step pyrolysis of molten urea and formaldehyde was adopted to introduce O atom, C and N defects in polymeric carbon nitride (CN) for tuning its electronic structures. Results confirmed that the introduced C, N-defects and O dopant could increase the light absorption (440–640 nm) and suppressed the photogenerated charge recombination of CN. The calculated free energies for H* adsorption revealed that the intrinsic H2 evolution activity of C, N-deficient and O-doped CN increased. Accordingly, the optimal sample exhibited an excellent photocatalytic H2 evolution rate (HER) of 18.95 mmol g−1 h−1 in 10% triethanolamine solution under visible light irradiation (1% Pt as a cocatalyst), which was 6.7 times higher than that of traditional CN (2.83 mmol g−1 h−1). In addition, the HER and yield of benzaldehyde were 1.04 and 4.20 mmol g−1 h−1, respectively in 5% benzyl alcohol solution. This work provides a simple and effective strategy to tune the heptazine and electronic structure of CN for large increasing its photocatalytic activity.

Catalytic Activity of Nonaggregating Cu Nanoparticles Supported in Pores of Zeolite for Aerobic Oxidation of Benzyl Alcohol.

Cu nanoparticles (NPs) as catalysts have the good advantage of being more abundant than noble metal NPs. In this study, we synthesized nonaggregating Cu NPs supported in Y-type zeolite by the photoreduction method. In this method, Cu ions in pores of zeolite can be slowly reduced with a small amount of reductant at room temperature. The high-resolution transmission electron microscope, energy dispersive X-ray spectroscopy, X-ray diffraction patterns, and UV-Vis spectra supported that nonaggregating Cu NPs existed in the pores of zeolite. Catalytic activities of Cu NP-zeolite were investigated for the aerobic oxidation of benzyl alcohol. Our Cu NP-zeolite had a large turnover frequency of 17 h-1. The yield of benzaldehyde increased in proportion to the amount of Cu loading at ≤0.5 wt %, indicating that Cu NPs in pores of zeolite work as catalysts for selective aerobic oxidation of benzyl alcohol. The high catalytic activity was brought by nonaggregating Cu NPs in pores of zeolite. The catalytic reaction for other aromatic alcohols with electron-donating groups proceeded, whereas it did not proceed for the aromatic alcohols with electron-withdrawing groups or aliphatic alcohols, indicating that the interaction between zeolite and the benzene ring also contributed to the reaction. This study would be expected to contribute to the development of Cu NP catalysts.

Full-spectrum responsive dual-defect mediated S-scheme heterojunction for cooperative benzyl alcohol conversion and H2 evolution

The construction of a dual system for photocatalytic redox reaction is an effective strategy to promote photocatalytic decomposition of water for H2 evolution, which not only overcomes the slow process of water oxidation during water decomposition but also combines with biomass conversion to produce high-value chemicals. Herein, three-dimensional full-spectrum responsive P–MoS2–ZnIn2S4–2 (P–M−Z−2) flower-like materials are prepared for efficient production of H2 coupled with benzyl alcohol oxidation by constructing S-scheme heterojunction and P-doping to modulate the sulfur vacancies. In this case, the hole trap P doping site and the electron trap sulfur vacancy have a synergistic effect of regulating the charge flow to realize the photogenerated carrier separation more effectively. The resulting P–M−Z−2 shows a remarkable photocatalytic effect (3763.2 μmol·h−1·g−1 for H2 evolution and almost 100 % yield of benzaldehyde) under visible light irradiation, which was about 9 times higher than that of pure ZnIn2S4. More importantly, the optimized P-M−Z−2 displays H2 evolution efficiency of 31423.6 μmol·h−1·g−1 and 31297.7 μmol·h−1·g−1 for benzaldehyde generation under simulated sunlight irradiation (AM 1.5G). The construction of S-scheme heterojunctions retains a higher redox potential for the catalysts, which improves the redox capacity and thus the photocatalytic performance, as well as the heterojunctions facilitate the separation and transport of photogenerated carriers. This work not only reveals the strategy to enhance the photocatalytic performance by doping modulation of sulfur vacancies and construction of S-scheme heterojunctions but also provides ideas for realizing efficient valorization of biomass platform compounds.

Highly Selective Oxidation of Toluene to Benzaldehyde in Alkaline Systems

For the selective oxidation of toluene to benzaldehyde, the biggest challenge is to prevent the further oxidation of benzaldehyde as toluene conversion increases. Using benzyl benzoate as the solvent and adding benzoate to adjust the alkalinity of the system, the formation of the benzoyl radical can be well inhibited, but the oxidation of toluene is weakened. The decomposition of benzyl benzoate to benzaldehyde can activate the reaction at the initial stage, and the negative influence of alkalinity is avoided to some extent. Therefore, by using atmospheric air as an oxidant, a high selectivity and yield of benzaldehyde can be obtained in a benzyl benzoate catalytic system with alkali as an additive. The mechanism of alkaline regulation and selective oxidation of toluene was investigated by in situ infrared (IR) spectroscopy experiments. The benzaldehyde capacity is defined to characterize the tolerance of benzaldehyde in the system. Catalysts and alkaline regulators can be easily reused with high-boiling solvents, making it a convenient process for product separation and catalyst–alkaline solvent recycling.

Synthesis of water soluble copper(II), manganese(III) phthalocyanines and their photocatalytic performances in benzyl alcohol photoxidation

In this study, peripherally tetra-{[4-(3,5-dichlorophenyl)-5-pyridin-4-yl-4H-1,2,4-triazol-3-yl]thio} group substituted cobalt(II), manganese(III) phthalocyanines (BS-1-Cu, BS-1-Mn) and their water soluble derivatives (BS-1-CuQ, BS-1-MnQ) were synthesized via multistep reactions. The structure of new compounds were characterized by FT-IR, 1H-NMR, 13-CNMR, Mass, and UV visible spectroscopy. Then, photocatalytic properties of water soluble phthalocyanines (BS-1-CuQ, BS-1-MnQ) were investigated in benzyl alcohol (BA) photoxidation reaction. Photocatalytic results indicate that the former has high benzaldehyde selectivity (93%) and the latter employees with high product conversion (83%) at the same reaction conditions. The same yield of benzaldehyde (59%) was calculated with both photocatalysts at room temperature in water. The photocatalytic activity of BS-1-CuQ and BS-1-MnQ was evaluated by changing substrate amount and oxidant type. Additionally, the degradation of the BA were investigated in the presence of 0.05 g catalyst, 100 ml 0.015 M BA solution, 25 °C, 15 min in water. The recycling studies indicated that BS-1-MnQ can be used after 4 cycles, BS-1-CuQ can be used even after 3 cycles.

Selective Oxidation of Toluene to Benzaldehyde Using Co-ZIF Nano-Catalyst

Nanometer-size Co-ZIF (zeolitic imidazolate frameworks) catalyst was prepared for selective oxidation of toluene to benzaldehyde under mild conditions. The typical characteristics of the metal-organic frameworks (MOFs) material were affirmed by the XRD, SEM, and TEM, the BET surface area of this catalyst was as high as 924.25 m2/g, and the diameter of particles was near 200 nm from TEM results. The Co metal was coated with 2-methyl glyoxaline, and the crystalline planes were relatively stable. The reaction temperatures, oxygen pressure, mass amount of N-hydroxyphthalimide (NHPI), and reaction time were discussed. The Co-ZIF catalyst gave the best result of 92.30% toluene conversion and 91.31% selectivity to benzaldehyde under 0.12 MPa and 313 K. The addition of a certain amount of NHPI and the smooth oxidate capacity of the catalyst were important factors in the high yield of benzaldehyde. This nanometer-size catalyst showed superior performance for recycling use in the oxidation of toluene. Finally, a possible reaction mechanism was proposed. This new nanometer-size Co-ZIF catalyst will be applied well in the selective oxidation of toluene to benzaldehyde.

Alkali metal ion assisted preparation of zeolite encapsulated small cobalt cluster CoOx for direct styrene oxidation to benzaldehyde

Zeolites with metal clusters encapsulated within the pore structure have attracted more attention because of their unique properties with high stability, but diffusion resistance is the bottleneck limiting the utilization efficiency of active centers, especially in macromolecular reactions. Hollow zeolites could effectively improve mass transport by reducing the wall thickness. In this work, cobalt-base hollow silicate-1 zeolite was obtained by mother liquid treatment with sodium chloride. Various characterization results show that the CoOx@HS-1-0.5Na+ crystals have completely hollow structure and small cobalt cluster highly dispersed encapsulated in it. The presence of Lewis acid sites and the unique hollow structure resulted in enhanced selectivity to benzaldehyde in the styrene oxidation. The effect of various factors including cobalt loading, the concentration of sodium ion, reaction solvents and H2O2/styrene molar ratio on the catalytic performance were systematically investigated. The yield of benzaldehyde can achieve 73.8% with 83.59% styrene conversion and 88.29% benzaldehyde selectivity.

Synthesis, Crystal Structure and Catalytic Activity of Tri-Nuclear Zn(II) Complex Based on 6-Phenylpyridine-2-carboxylic Acid and Bis(4-pyridyl)amine Ligands

A new trinuclear Zn (II) complex, [Zn3(L1)4(L2)2(CH3COO)2] (1) (HL1 = 6-phenylpyridine-2-carboxylic acid, L2 = bis(4-pyridyl)amine) has been synthesized by 6-phenylpyridine-2-carboxylic acid, NaOH, bis(4-pyridyl)amine and Zn(CH3COO)2•2H2O. The complex 1 has also been structural characterized by elemental analysis and single crystal X-ray diffraction. The results reveals that complex 1 is made up of three Zn(II) ions, four L1 ligands, two L2 ligands and two CH3COO- anions. In 1, both Zn1 ion and Zn1a ion are five-coordinated with two O atoms from two different L1 ligands, two N atoms from two different L1 ligands, and one N atoms from bis(4-pyridyl)amine ligand, respectively, and forms a distorted trigonal biyramid geometry. And Zn2 ion is four-coordinated with two O atoms from two different CH3COO− anions and two N atoms from two different L2 ligands, forming a distorted tetrahedral geometry. Complex 1 displays a 3D network structure by the intermolecular N−H···O hydrogen bonds. The catalytic performance for oxidation of benzyl alcohol with O2 was studied under mild reaction conditions using complex 1 as catalyst. The results demonstrated that the catalysts were very active, and the yield of benzaldehyde was 50.8% at 90 °C with THF as solvent under 0.5 MPa O2 within 3 h. Copyright © 2022 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Interfacial synthesis of Co-based ultrathin nanosheets with NaF crystal as template and inducer: fluorine doped Co(OH)2, porous fluorine doped Co3O4, and porous Co3O4

NaF crystals were used as the template and inducer, and fluorine doped cobalt hydroxy ultrathin nanosheets (F-Co(OH)2) were synthesized at room temperature. F-Co(OH)2 exhibits a petal-like morphology with a thickness of ∼1.7 nm. Porous fluorine doped Co3O4 ultrathin nanosheets (pF-Co3O4) and porous Co3O4 ultrathin nanosheets (p-Co3O4) were synthesized through the calcinations of F-Co(OH)2 at 230 °C and 330 °C, respectively. They exhibit a petal-like morphology with a thickness of ∼1.6 nm. pF-Co3O4 and p-Co3O4 have been applied for the catalytic oxidation benzyl alcohol. At the identical conditions, pF-Co3O4 achieved 100% benzyl alcohol conversion and 100% yield of benzaldehyde, and p-Co3O4 achieved 100% benzyl alcohol with 69.8% yield of benzaldehyde and 30.2% yield of benzoic acid. For the oxidation benzyl alcohol, both pF-Co3O4 and p-Co3O4 have exhibited much higher catalytic efficiencies than bulk Co3O4.

Self-supported hierarchical crystalline carbon nitride arrays with triazine-heptazine heterojunctions for highly efficient photoredox catalysis

Self-supported hierarchical crystalline carbon nitride arrays (MA-rod array), which show the excellent properties of photocatalytic hydrogen evolution and oxidative organic synthesis, were synthesized by molten salt-assisted pyrolysis of rod-like supramolecular precursors from the hydrolysis of melamine. On the nanoscale, the highly crystalline MA-rod array has an omasum-like architecture with combined advantages of rapid electrolyte diffusion, efficient gas evolution, fast electronic transmission, and lower interface resistance. At the molecular level, the triazine-heptazine heterojunctions remarkably improve charge carrier transfer and separation. In the tests of photoredox catalysis, the MA-rod array exhibited 51-fold higher hydrogen production rate (11720 μmol h−1 gcat-1) than the reference with a high apparent quantum yield (AQY) of 60% at 420 nm. Furthermore, the oxidation of aromatic hydrocarbons to aldehydes or ketones can be obtained under single wavelength (460 nm) irradiation with milligram yields (e.g., the isolated yield of benzaldehyde is 34.5 mg with the conversion rate of 1805.6 μmol h−1 gcat-1), surpassing other photocatalysts so far.

Functional mimic for amine and catechol oxidases: Structural, spectral, electrochemical and catalytic properties of mononuclear copper(II) complex

A mononuclear copper(II) complex, [Cu(L)(Hdpa)](ClO4) (where H(L) is 1-(2-diethylamino)- ethyliminomethyl)naphthol, the tridentate N,N,O-donor Schiff base formed by 2-hydroxy-1-naphthaldehyde and N,N’-diethylethylenediamine and Hdpa is 2,2′-dipyridylamine) have been synthesized and structurally characterized by different spectral and electrochemical methods including single crystal X-ray diffraction study. The Cu(II) center in the complex adopts a square pyramidal geometry with an N4O coordination environment. It exhibits inter-pair dimeric association in its solid-state due to (a) inter-pair π-π interactions, (b) intermolecular NH⋯O hydrogen bonding, and (c) CH⋯π non-covalent interactions and it is weakened in solution. The complex shows a reversible one-electron redox process (Cu(II) ⇌ Cu(I)) with high positive potential. The benzylamine was used as the substrate in methanol solution, revealing that the complex exhibits greater catalytic activity with an 83% isolated yield of benzaldehyde. Also, the complex effectively catalyze the oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) in methanol (M) and buffer solution (BS, pH 7.0) to the corresponding 3,5-di-tert-butyl-o-quinone (3,5-DTBQ) with significant turnover number, Kcat (h−1) = 1.96 × 103 (M) and 2.26 × 105 (BS), which are comparable to the best values reported in the literature. The complex mimics the functional activities of both amine and catechol oxidases and can thus be regarded as models.

POM-incorporated ZnIn2S4 Z-scheme dual-functional photocatalysts for cooperative benzyl alcohol oxidation and H2 evolution in aqueous solution

Efficient aromatic alcohol oxidation with simultaneous H2 evolution under aqueous conditions is achieved in a polyoxometalate (POM)-incorporated ZnIn2S4 dual-functional photocatalytic system. The synergy between HPM and ZIS contributes to the formation of a Z-type heterojunction structure and thus enhances redox capacity. Moreover, the sub-nanometer size of POM clusters endows molecular-level interfacial contact, which acts as an "electron bridge" ensuring faster interfacial charge transfer kinetics. Therefore, an impressive nearly 100% yield of benzaldehyde and 10.6 mmol·g−1·h−1 H2-evolution rate are observed for POM/ZIS nanocomposites even under an anaerobic atmosphere with water as the solvent. This is the first application of POM-based materials in the anaerobic oxidation of benzyl alcohol with concomitant H2 production. This study expands the possibilities for designing multifunctional POM-based photocatalysts for economic and ecological photoredox applications.

Accelerating Anode Reaction with Electro-oxidation of Alcohols over Ru Nanoparticles to Reduce the Potential for Water Splitting.

Generating hydrogen by water electrolysis is a promising and sustainable approach to the production of a green energy carrier, but the sluggish kinetics of the oxygen evolution reaction (OER) at anode leads to a high working potential. Replacing OER with electro-oxidation of organics driven at a low potential offers an effective way to accelerate the sluggish anode reaction, and thus increase hydrogen evolution in water-splitting. Herein, we have prepared a Ru nanoparticles on N-doped carbon nanotubes (Ru-NPs@NCNTs) to implement electro-oxidation of benzyl alcohol toward reducing the anodic potential in watersplitting. The potential of the anode reaction is remarkably decreased from 1.76 to 1.19 V vs RHE at a current density of 10 mA cm-2 with the assistance of a Ru-NPs catalyst. Furthermore, 100% selectivity and 95% yield of valuable benzaldehyde were achieved simultaneously. The Ru-NPs also exhibits good durability and wide applicability to other alcohols. The high performance of Ru-NPs is mainly attributed to the unique horizontal adsorption configuration of benzyl alcohol with surface atoms of the catalyst, shortening the distance between the •OH group and Ru atoms, and increasing the activation rate of the •OH group. This work presents a feasible strategy to boost water-splitting performance and concurrently produce value-added organics under mild conditions.