Production Of Benzaldehyde Research Articles

The Combination of Graphitic Carbon Nitride (gC3N4) and Supercritical Carbon Dioxide for Green Photooxidation of Benzylic Alcohols

AbstractThe research focuses on the innovative use of graphite‐like carbon nitride (gC3N4) catalysts along with supercritical carbon dioxide (scCO2) for the green synthesis of valuable organic compounds. Having explored different synthetic routes for gC3N4 and the obtained samples efficiency in the photocatalytic oxidation of benzyl alcohol with molecular oxygen in scCO2, we identified the most effective catalyst bearing ether linkers between layers of a graphite‐like structure. This catalyst facilitates the production of benzaldehyde and benzoic acid derivatives, highlighting the potential for sustainable industrial applications. The study's emphasis on a metal‐free catalyst and a zero‐waste process underlines its contribution to environmentally friendly chemical practices. The proposed approach offers a more sustainable and efficient alternative to traditional processes in small‐scale chemical production.

Surface engineering of TeOx modification on MoVTeNbO creates a high-performance catalyst for oxidation of toluene homologues to aldehydes

The heterogeneous catalytic oxidation of toluene by O2 is an inherently safe and green route for production of benzaldehyde, but after more than fifty years of effort, it remains a great challenge. Here, we report the best heterogeneous catalyst, TeOx/MoVTeNbO, up to now for the green oxidation of toluene by O2 to benzaldehyde, balancing the catalyst activity, selectivity, and stability. The deposition of TeOx endows the MoVTeNbO composite oxide with entirely new property for toluene oxidation and the surface engineering mechanism has been fully explained. The discrete TeOx clusters on the surface, shielding the nonselective oxidation sites that interact strongly with the benzene ring of toluene molecule, allows toluene molecule to chemically adsorb to the surface perpendicularly and the methyl is then prone to oxidation to aldehyde on the reshaped selective oxidation sites, where V=O is the main active species responsible for continuously extracting hydrogen from methyl and implanting oxygen to form benzaldehyde. The TeOx clusters participate in this reaction through variable valences and stabilize benzaldehyde by couple interaction with the –CHO group of benzaldehyde, thereby achieving high selectivity to benzaldehyde (>95%). The extended works indicate that the catalytic mechanism is effective in a series of selective oxidation of toluene homologues to corresponding aldehydes.

Surfactants govern the fabrication of sulfur-enriched heterojunction catalysts for highly selective photocatalytic conversion of toluene

Photocatalytic selective oxidation of toluene represents a milder and more environmentally friendly strategy for the synthesis of benzaldehyde. In order to enhance catalytic performance, efficient carrier separation and transport are crucial in the photocatalytic process. This study focused on the preparation of ZnS@ZnIn2S4 with sulfur vacancies and heterostructures, combining the advantages properties of ZnS and ZnIn2S4 in photocatalysis. The effects of ZnS and surfactants on the catalytic properties of the composites were studied in depth. Characterization tests revealed that surfactant-modified ZnS@ZnIn2S4 exhibited a higher concentration of sulfur defects, which facilitated electron trapping and promoted photogenerated carrier separation and utilization. Additionally, the present study also demonstrated that the incorporation of ZnS and surfactants could reduce the crystal size of ZnIn2S4, thereby facilitating the exposure of additional active sites. The synergistic effect of the aforementioned advantages enabled toluene to undergo oxidation at a conversion rate of 39% in the presence of oxygen, resulting in the production of benzaldehyde with an exceptional selectivity of 92%. This finding offers valuable insights for future endeavors in designing photocatalytic C-H bond oxidation catalysts.

Sodium thiosulfate modified graphitic carbon nitride for enhancing the photocatalytic production of aldehydes

The oxidation of alcohols to aldehydes is one of the most relevant reactions in organic chemistry. The currently implemented methods based on expensive noble metallic catalysts, toxic solvents, and high temperature and pressure conditions have released the seek for softer and cheaper alternatives such as photocatalysis. In this sense, graphitic carbon nitride has been modified with sodium thiosulfate as a source of S and Na+ incorporation in the structure, aimed at enhancing the photocatalytic performance on the oxidation of alcohols to aldehydes, i.e. cinnamaldehyde, benzaldehyde, and vanillin in aqueous solution. Three g-C3N4 samples synthesized from different precursors, i.e. melamine, thiourea, and urea, were treated with sodium thiosulfate. Urea led to the g-C3N4 with the highest mesoporosity (surface area, 69 m2 g−1) and photocatalytic activity. The modification with 5 % (wt.) of Na2S2O3 enhanced the pseudo-first order rate constant of cinnamyl alcohol oxidation from 0.265 h−1 (bare sample) to 0.792 h−1 (Na2S2O3-modified). The characterization of the material suggests a better charge separation of the photogenerated charges after S and Na+ incorporation in the structure, minimizing the recombination rate of photogenerated charges. The optimum photocatalyst, tested in aqueous solution, was most selective in the production of benzaldehyde (selectivity, >100 %) > cinnamaldehyde (>23 %) > vanillin (∼5 %). The selectivity was considerably boosted under acetonitrile as the solvent medium, raising in the case of cinnamaldehyde the 23 % recorded in water to 51 % in pure acetonitrile. The degradation mechanism suggests a strong influence of the photogenerated holes and the superoxide radical, the latter being more selective in the oxidation of the alcohol.

Microbiomics and metabolomics insights into the microbial regulation on the formation of flavor components in the traditional fermentation process of Chinese Hongqu aged vinegar

This study aimed to investigate microbial succession and metabolic dynamics during the traditional fermentation of Hongqu aged vinegar, and explore the core functional microbes closely related to the formation of flavor components. Microbiome analysis demonstrated that Lactobacillus, Acetobacter, Bacillus, Enterobacter, Lactococcus, Leuconostoc and Weissella were the predominant bacterial genera, while Aspergillus piperis, Aspergillus oryzae, Monascus purpureus, Candida athensensis, C. xylopsoci, Penicillium ochrosalmoneum and Simplicillium aogashimaense were the predominant fungal species. Correlation analysis revealed that Acetobacter was positively correlated with the production of tetramethylpyrazine, acetoin and acetic acid, Lactococcus showed positive correlation with the production of 2-nonanone, 2-heptanone, ethyl caprylate, ethyl caprate, 1-hexanol, 1-octanol and 1-octen-3-ol, C. xylopsoci and C. rugosa were positively associated with the production of diethyl malonate, 2,3-butanediyl diacetate, acetoin, benzaldehyde and tetramethylpyrazine. Correspondingly, non-volatile metabolites were also detected through ultra-performance liquid chromatography-quadrupole time-of-flight mass spectrometry. A variety of amino acids and functional dipeptides were identified during the traditional brewing of Hongqu aged vinegar. Correlation analysis revealed that Lactobacillus was significantly associated with DL-lactate, indolelactic acid, D-(+)-3-phenyllactic acid, pimelic acid, pregabalin and 3-aminobutanoic acid. This study is useful for understanding flavor formation mechanism and developing effective strategies for the suitable strains selection to improve the flavor quality of Hongqu aged vinegar.

Ultrathin 2D[sbnd]2D WO3-x-C3N4 heterostructure-based high-efficiency photocatalyst for selective oxidation of toluene

Photocatalytic oxidation of toluene for the organic synthesis of value-added benzaldehyde has attracted great attention in recent years. However, activation of CH bonds and selective production of benzaldehyde under mild green conditions remains a great challenge. Herein, a series of two-dimensional (2D) ultrathin heterostructure-based components (WO3-x-C3N4 nanosheets), fabricated by coupling oxygen-deficient WO3-x with amorphous C3N4 via a simple electrostatic self-assembly method, was demonstrated as high-efficiency photocatalysts to produce benzaldehyde in the presence O2 as oxidant at room temperature. Under optimal conditions, the prepared 10WCN sample (10 wt% WO3-x-C3N4) exhibited improved photocatalytic oxidation ability with a good benzaldehyde selectivity (96 %) and high benzaldehyde yield (2738.6 μmol g−1 h−1) within 6 h, which is 6.6 and 3.3 times than that of pure WO3-x (412.5 μmol g−1 h−1) and C3N4 (835.7 μmol g−1 h−1). The enhanced photocatalytic performance was due to the constructed 2D type II heterojunction and abundant oxygen vacancies (OVs), contributing to the photoinduced carriers' separation and migration efficiently. This work indicates the synergistic effect of defect metal oxides and 2D ultrathin sheet-to-sheet heterojunctions in photocatalytic hydrocarbon conversion.

Structure-driven development of a biomimetic rare earth artificial metalloprotein

The 2011 discovery of the first rare earth-dependent enzyme in methylotrophic Methylobacterium extorquens AM1 prompted intensive research toward understanding the unique chemistry at play in these systems. This enzyme, an alcohol dehydrogenase (ADH), features a La3+ ion closely associated with redox-active coenzyme pyrroloquinoline quinone (PQQ) and is structurally homologous to the Ca2+-dependent ADH from the same organism. AM1 also produces a periplasmic PQQ-binding protein, PqqT, which we have now structurally characterized to 1.46-Å resolution by X-ray diffraction. This crystal structure reveals a Lys residue hydrogen-bonded to PQQ at the site analogously occupied by a Lewis acidic cation in ADH. Accordingly, we prepared K142A- and K142D-PqqT variants to assess the relevance of this site toward metal binding. Isothermal titration calorimetry experiments and titrations monitored by UV-Vis absorption and emission spectroscopies support that K142D-PqqT binds tightly (Kd = 0.6 ± 0.2 μM) to La3+ in the presence of bound PQQ and produces spectral signatures consistent with those of ADH enzymes. These spectral signatures are not observed for WT- or K142A-variants or upon addition of Ca2+ to PQQ ⸦ K142D-PqqT. Addition of benzyl alcohol to La3+-bound PQQ ⸦ K142D-PqqT (but not Ca2+-bound PQQ ⸦ K142D-PqqT, or La3+-bound PQQ ⸦ WT-PqqT) produces spectroscopic changes associated with PQQ reduction, and chemical trapping experiments reveal the production of benzaldehyde, supporting ADH activity. By creating a metal binding site that mimics native ADH enzymes, we present a rare earth-dependent artificial metalloenzyme primed for future mechanistic, biocatalytic, and biosensing applications.

Electron Tandem Transport Channel in a Cu3P/Sv-ZnIn2S4 p-n Heterojunction for Photothermal-Photocatalytic Benzyl Alcohol Oxidation and H2 Production.

The development of photocatalytic systems with an electron tandem transport channel represents a promising avenue for improving the utilization of photogenerated electrons and holes despite encountering significant challenges. In this study, ZnIn2S4 (Sv-ZIS) with sulfur vacancies was fabricated using a solvothermal technique to create defect energy levels. Subsequently, Cu3P nanoparticles were coupled onto the surface of Sv-ZIS, forming a Cu3P/Sv-ZIS p-n heterojunction with an electron tandem transport channel. Experimental findings demonstrated that this tandem transport channel enhanced the carrier lifetime and separation efficiency. In addition, mechanistic investigations unveiled the formation of a robust built-in electric field (BEF) at the interface between Cu3P and Sv-ZIS, providing a driving force for electron migration. The combined consequences of the transport channel, the strong BEF, and photothermal effect led to a surface carrier separation efficiency of 65.85%. Consequently, Cu3P/Sv-ZIS achieved simultaneous H2 yield and benzaldehyde production rates of 18,101.4 and 15,012.6 μmol·g-1·h-1, which were 2.31 and 2.62 times higher than those of ZnIn2S4, respectively. This work exemplifies the design of the p-n heterojunction for the efficient utilization of photogenerated electrons and holes.

S-scheme TiO2/Bi2WO6 heterojunction for enhanced photocatalytic selective oxidation of toluene

Selective activation of saturated C–H bonds in hydrocarbons, such as the activation of the C–H bond in toluene, is an effective method for the production of high value-added chemicals. However, improving the C–H bond activation of toluene remains a challenge. In this study, S-scheme TiO2/Bi2WO6 composites were synthesized by loading TiO2 nanoparticles on Bi2WO6 flakes using a simple hydrothermal method. The physical and chemical properties of the prepared materials were characterized using X-Ray Diffraction (XRD), Fourier Transform Infrared Spectoscopy (FT-IR), Scanning Electronic Microscopy (SEM), X-ray Photoelectron Spectroscopy (XPS) and other characterization methods. Selective oxidation of toluene to benzaldehyde under visible light irradiation using air as an oxidizing agent. When the molar ratio of TiO2 and Bi2WO6 was 0.20, the composites exhibited excellent photocatalytic performance with a benzaldehyde production rate of 1725.41 μmol g−1 h−1, which was 2.31 and 1.91 times higher than that of TiO2 and Bi2WO6, respectively. This excellent performance is attributed to the formation of heterojunction structure by the loaded TiO2 nanoparticles, which improves the separation efficiency of photogenerated carriers and thus enhances its photocatalytic performance. In addition, the active substances involved in the photocatalytic reaction were identified by free radical trapping experiments as ·O2− and h+. Finally, the photocatalytic mechanism of S-scheme TiO2/Bi2WO6 composites was proposed by energy band structure analysis and radical trapping experiments. This study provides a simple design pathway for the construction of visible-light responsive bismuth tungstate-based heterojunction photocatalysts and some ideas for the development of new and efficient photocatalytic toluene selective oxidation catalysts.

An Investigation of N-Hydroxyphthalimide Catalyzed Aerobic Oxidation of Toluene without Metal Ions in Liquid Phase: Effect of Solvents and Phase Transfer Catalysts.

The selective oxidation of toluene to yield value-added oxygenates, such as benzyl alcohol, benzaldehyde, and benzoic acid, via dioxygen presents a chlorine-free approach under benign conditions. Metal-free catalytic processes are preferred to avoid metal ion contamination. In this study, we employed N-hydroxyphthalimide (NHPI) as a catalyst for the aerobic oxidation of toluene to its oxygenated derivatives. The choice of solvent exerted a significant impact on the catalytic activity and selectivity of the catalyst NHPI at reaction temperatures exceeding 70 °C. Notably, hexafluoroisopropanol substantially enhanced the selective production of benzaldehyde. Furthermore, we identified didecyl dimethyl ammonium bromide, featuring two symmetrical long hydrophobic chains, as a potent enhancer of NHPI for the solvent-free aerobic oxidation of toluene. This effect is ascribed to its unique symmetrical structure, extraction capabilities, and resistance to thermal and acid/base conditions. Based on the product distribution and control experiments, we proposed a plausible reaction mechanism. These findings may inform the industrial synthesis of oxygenated derivatives from toluene.

Design and fabrication of a novel 2D/3D ZnIn2S4@Ni1/UiO-66-NH2 heterojunction for highly efficient visible-light photocatalytic H2 evolution coupled with benzyl alcohol valorization

Making full use of photogenerated charge carriers by careful design multifunctional photocatalysts to achieving bi-value-added production with high-efficiency is highly desirable and extremely challenge. Herein, a novel 2D/3D ZnIn2S4@Ni1/UiO-66-NH2 (ZIS@Ni1/UN) heterojunction with spatially separated and precise redox sites was designed and fabricated for both photocatalytic H2 production and benzyl alcohol (BA) valorization. By precise structural regulation and modification of UiO-66 integrated with -NH2, ZnIn2S4 (ZIS) and Ni single-atom, the spatial separation of redox sites and directional electron transfer has been achieved. This realizes collaborative and efficient solar energy to chemical energy conversion. The optimal sample 5ZIS@Ni1/UN-6 shows high photocatalytic H2 and benzaldehyde (BAD) production rates of 11.44 mmol∙g−1∙h−1 and 10.02 mmol∙g−1∙h−1 under visible light. This work highlights the importance of rational construction for the engineering of charge behavior in heterogeneous photocatalysts with spatial separation and identifies their crucial role in promoting the photocatalytic redox coupling reactions.

Surface decoration of plasmonic Ag nanospheres for enhanced visible light photocatalysis of BiVO4

The industrial concern of producing benzaldehyde (BD) more efficiently is the key aspect of this work. Therefore, the oxidation of benzyl alcohol (BA) by photocatalytic route was chosen. The amoeba-like BiVO4 (BV) particles were synthesized by co-precipitate method since it gives higher yield when compared to other methods and silver nanoparticles were decorated over its surface by photo deposition method. Due to surface plasmon resonance (SPR effect), the decorated samples showed enhanced optoelectronic properties. The band edge positions shifted to higher energy levels profitably paving the way for the production of superoxide radicals (•O2−) effectively. The optimal catalyst material was engineered in such a way that it would facilitate the production of both •O2− and BA* radicals and inhibits the production of BD* radical. The decorated silver nanoparticles aided in increasing the surface area and the number of catalytic active sites, therein a 4.7-fold increase in benzaldehyde yield was achieved when compared to pure BV. Since monoclinic BV possesses piezoelectric property, the use of ultrasound in the reaction medium boosted the efficiency of the reaction and henceforth a maximum conversion of 88.29 % was obtained. Hydrogen peroxide formed as a byproduct, adds commercial value to this reaction.

2D/2D homojunction-mediated charge separation: Synergistic effect of crystalline C3N5 and g-C3N4 via electrostatic self-assembly for photocatalytic hydrogen and benzaldehyde production

Homojunction engineering is a promising modification strategy to improve charge carrier separation and photocatalytic performance of carbon nitrides. Leveraging intrinsic heptazine/triazine phase and face-to-face contact, crystalline C3N5 (CC3N5) was combined with protonated g-C3N4 (pgCN) through electrostatic self-assembly to achieve robust 2D/2D homojunction interfaces. The highest photocatalytic performance was obtained through crystallinity and homojunction engineering, by controlling the pgCN:CC3N5 ratio. The 25:100 pgCN:CC3N5 homojunction (25CgCN) had the highest hydrogen production (1409.51 μmol h−1) and apparent quantum efficiency (25.04%, 420 nm), 8-fold and 180-fold higher than CC3N5 and pgCN, respectively. This photocatalytic homojunction improves benzaldehyde and hydrogen production activity, retaining 89% performance after 3 cycles (12 h) on a 3D-printed substrate. Electron paramagnetic resonance demonstrated higher ·OH−, ·O2− and hole production of irradiated 25CgCN, attributed to crystallinity and homojunction interaction. Thus, electrostatic self-assembly to couple CC3N5 and pgCN in a 2D/2D homojunction interface ameliorates the performance of multifunctional solar-driven applications.

Facile preparation and catalytic property of a sandwich composite membrane

Membrane as a support for metal nanocatalysts, can greatly enhance the catalytic activity of metal nanoparticles and promote the efficient production and separation of products. In this study, a novel sandwich-structured composite membrane was designed and facilely fabricated by using palladium nanocatalysts as the core catalytic layer and two different structured PVDF layers as the outer layers. The composite membrane was used as a reaction interface as well as a separation barrier between reactants and products, efficiently realizing the catalytic oxidation of benzyl alcohol and convenient separation of the product benzaldehyde. The membrane was characterized in detailed and the effects of the membrane structure and various reaction conditions on the catalytic oxidation were systematically investigated. The results indicated that the reaction could be conveniently carried out under very mild experimental conditions, obtaining the product benzaldehyde at as high selectivity as 93.17 %. The successful implementation of the sandwich membrane for the production of chlorine-free benzaldehyde provides a new method for the interface reaction.

Full-Space Electric Field in Mo-Decorated Zn2In2S5 Polarization Photocatalyst for Oriented Charge Flow and Efficient Hydrogen Production.

Integration of photocatalytic hydrogen (H2) evolution with oxidative organic synthesis presents a highly attractive strategy for the simultaneous production of clean H2 fuel and high-value chemicals. However, the sluggish dynamics of photogenerated charge carriers across the photocatalysts result in low photoconversion efficiency, hindering the wide applications of such a technology. Herein, this work overcomes this limitation by inducing the full-space electric field via charge polarization engineering on a Mo cluster-decorated Zn2In2S5 (Mo-Zn2In2S5) photocatalyst. Specifically, this full-space electric field arises from a cascade of the bulk electric field (BEF) and local surface electric field (LSEF), triggering the oriented migration of photogenerated electrons from [Zn-S] regions to [In-S] regions and eventually to Mo cluster sites, ensuring efficient separation of bulk and surface charge carriers. Moreover, the surface Mo clusters induce a tip enhancement effect to optimize charge transfer behavior by augmenting electrons and proton concentration around the active sites on the basal plane of Zn2In2S5. Notably, the optimized Mo1.5-Zn2In2S5 catalyst achieves exceptional H2 and benzaldehyde production rates of 34.35 and 45.31mmol gcat -1 h-1, respectively, outperforming pristine ZnIn2S4 by 3.83- and 4.15-fold. These findings mark a significant stride in steering charge flow for enhanced photocatalytic performance.

Phosphotungstic Acid Clusters Decorated Znln2S4 Nanoflowers as Molecular-Scale S-Scheme Heterojunctions for Simultaneous H2 Evolution and Benzyl Alcohol Upgrading.

Simultaneous utilization of photogenerated electrons and holes to achieve overall redox reactions is attractive but still far from practical application. The emerging step (S)-scheme mechanism has proven to be an ideal approach to inhibit charge recombination and supply photoinduced charges with highest redox potentials. Herein, a hierarchical phosphotungstic acid (H3PW12O40, HPW)@Znln2S4 (ZISW) heterojunction was prepared through one-pot hydrothermal method for simultaneous hydrogen (H2) evolution and benzyl alcohol upgrading. The fabricated HPW-based heterojunctions indicated much enhanced visible-light absorption, promoted photogenerated charge transfer and inhibited charge recombination, owing to hierarchical architecture based on visible-light responsive Znln2S4 microspheres, and S-scheme charge transfer pathway. The S-scheme mechanism was further verified by free-radical trapping electron spin resonance (ESR) spectra. Moreover, the wettability of composite heterojunction was improved by the modification of hydrophilic HPW, contributing to gaining active hydrogen (H+) from water sustainably. The optimal ZISW-30 heterojunction photocatalyst indicated an enhanced hydrogen evolution rate of 27.59 mmol g-1 h-1 in benzyl alcohol (10 vol. %) solution under full-spectrum irradiation, along with highest benzaldehyde production rate is 8.32 mmol g-1 h-1. This work provides a promising guideline for incorporating HPW into S-scheme heterojunctions to achieve efficient overall redox reactions.

Application of Model-Free and Model-Based Kinetic Methods in Evaluation of Reactions Complexity during Thermo-Oxidative Degradation Process: Case Study of [4-(Hydroxymethyl)phenoxymethyl] Polystyrene Resin

This work examined the possibilities and limitations of model-free and model-based methods related to decrypting the kinetic complexity of multi-step thermo-oxidative degradation processes (as a testing system, a [4-(hydroxymethyl)phenoxymethyl] polystyrene resin was used), monitored by thermal analysis (TGA-DTG-DTA) techniques. It was found that isoconversional methods could successfully determine the correct number of process stages and presence of multiple reactions based on derived Ea(α) profiles and identify the negative dependence of the rate constant on the temperature. These methods could not overcome the problem that arose due to mass transfer limitations. The model-based method overcame more successfully the problem associated with mass transfer because its calculation machinery had capabilities for the correct solution of the total mass balance equation. However, a perfect fit with the experimental data was not achieved due to the dependence on the thermal history of the contribution (ctb.) of a given reaction step inside a fitting procedure cycle. On the other hand, through this approach, it was possible to estimate the rate-controlling steps of the process regarding the influence of the heating rate. It was found that for consecutive reaction mechanisms, the production of benzaldehyde and gases in high yields was controlled by the heating rate, where low heating rates were strongly recommended (≤10 K/min). Also, it was shown that the transport phenomenon may be also the rate-determining step (within the set of “intrinsic” kinetic parameters). It was also established that external heat transfer controls the overall rate, where the “pure” kinetic control regime had not been reached but was approached when lowering the temperature and size of the resin particles.

Construction of a bifunctional BiVO4 based S-scheme heterojunction for enhancing photothermal-photocatalytic oxygen generation and benzaldehyde production

In order to address the main challenges in photocatalysis, such as the recombination of photo-generated carriers and the limited absorption range of light, a successful strategy was developed by creating a photothermal-photocatalytic S-scheme heterojunction through the combination of CdS nanoparticles with BiVO4 nanorods. XPS analysis, as well as SPV results, revealed the establishment, direction, and strength of the internal electric field (IEF) in the created CdS/BiVO4 heterojunction. Due to the matched band structure and the strong IEF, the heterojunction followed the S-scheme transfer mode under light, inducing the strong redox ability and fast separation of photo-generated carriers. Besides that, the heat generated by incorporating a photothermal-effect during illumination also helped to boost the photocatalytic reaction. As a result, the engineered CdS/BiVO4 heterojunction exhibited an impressive benzaldehyde production of 17.45 mmol g−1·h−1, approximately four times higher than that of pure BiVO4 (3.70 mmol g−1·h−1). Furthermore, the oxygen evolution rate of the CdS/BiVO4 heterojunction was 3146.68 µmol·g−1, much higher than that of BiVO4 (1042.98 µmol·g−1). This study introduces a novel approach to overcome the fundamental obstacles in semiconductor photocatalysis, paving the way for enhanced overall performance.

Significant augmentation of hydrogen and benzaldehyde production through mediator-free in-situ synthesis of CuNi/CN photocatalysts for benzyl alcohol splitting

Amidst growing concerns surrounding global warming and energy scarcity, there is an urgent demand for more efficient and environmentally friendly methods of hydrogen production. In response, we introduce a novel mediator-free in-situ approach for synthesizing CuNi/CN composite photocatalysts. This method entails the synthesis of copper and nickel complexes to fabricate bimetallic Cu and Ni nanoparticles on carbon nitride (CN). These catalysts are deployed for the photocatalytic dehydrogenation of benzyl alcohol, resulting in the generation of hydrogen and benzaldehyde. The CuNi bimetal-loaded CN structure provides ample active sites and demonstrates a low hydrogen reduction overpotential, thereby enhancing both charge separation and surface hydrogen reduction processes. In comparison to pure CN, the composite photocatalyst exhibits significantly improved photocatalytic activity. Notably, the composite 2 % Cu1Ni1/CN photocatalyst achieves a record-high hydrogen production rate of about 80 μmol g-1h−1, representing an impressive increase of approximately 533 times compared to pristine CN. Moreover, the catalyst offers cost-effectiveness, ease of preparation, and reusability, ensuring stable hydrogen production efficiency over multiple cycles. This precious metal-free composite photocatalyst not only facilitates the synthesis of valuable compounds but also promotes sustainable advancements in efficient hydrogen energy generation.

Electrochemical oxidation of concentrated benzyl alcohol to high-purity benzaldehyde via superwetting organic-solid-water interfaces.

Organic electrosynthesis in aqueous media is presently hampered by the poor solubility of many organic reactants and thus low purity of liquid products in electrolytes. Using the electrooxidation of benzyl alcohol (BA) as a model reaction, we present a "sandwich-type" organic-solid-water (OSW) system, consisting of BA organic phase, KOH aqueous electrolyte, and porous anodes with Janus-like superwettability. The system allows independent diffusion of BA molecules from the organic phase to electrocatalytic active sites, enabling efficient electrooxidation of high-concentration BA to benzaldehyde (97% Faradaic efficiency at ~180 mA cm-2) with substantially reduced ohmic loss compared to conventional solid-liquid systems. The confined organic-water boundary within the electrode channels suppresses the interdiffusion of molecules and ions into the counterphase, thus preventing the hydration and overoxidation of benzaldehyde during long-term electrocatalysis. As a result, the direct production of high-purity benzaldehyde (91.7%) is achieved in a flow cell, showcasing the effectiveness of electrocatalysis over OSW interfaces for the one-step synthesis of high-purity organic compounds.