Photocatalytic Methanol Dehydrogenation with Switchable Selectivity

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 13, 2025

Switchable selectivity achieved by altering reaction conditions within the same photocatalytic system offers great advantages for sustainable chemical transformations and renewable energy conversion. In this study, we investigate an efficient methanol dehydrogenation with controlled varying concentration of nickel cocatalyst, using zinc indium sulfide nanocrystals as a semiconductor photocatalyst, which enables production either formaldehyde or ethylene glycol high selectivity. Control experiments revealed that is initially generated can serve terminal product intermediate in producing glycol, depending on solution. Mechanistic studies suggest unique role ionic additional photoelectron competitor significantly influence selectivity, alongside its well-established function hydrogen evolution cocatalyst under conditions. The demonstrated switchable provides new tool diverse products from methanol, while advancing understanding behavior versatile catalytic performance.

Language: Английский

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Electrocatalytic N–C–N coupling over a hierarchically ordered open single-atom superstructure toward organonitrogen synthesis

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: April 15, 2025

Electrochemically constructing C-N and N-C-N bonds provides an economical sustainable alternative to conventional chemosynthesis. Herein, a hierarchically ordered open superstructure of N-doped carbon isolated with accessible three-coordinated Zn single-atom sites is explored for efficient electrocatalytic coupling. Benefiting from the distinctive structural merits, this catalyst enables preparation bonded compounds methanol amines. Notably, Faradaic efficiency selectivity N,N,N',N'-tetramethyldiaminomethane reach up 77% 96% at 0.8 V, respectively. Further integrating aminoalkylation reaction, electro-thermo cascade synthesis electrochemically obtained serving as unique reagent, leading specific set organonitrogen (dimethylamino)methyl substituent, including topotecan hydrochloride, anti-tumor drug, high yield 95%. Furthermore, in situ spectroscopic characterization calculations unveil that under-coordinated Zn-N3 play pivotal role stabilizing key *CH2O intermediate, thereby facilitating subsequent nucleophilic addition

Language: Английский

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A Highly Efficient Electrosynthesis of Formaldehyde Using a TEMPO‐Based Polymer Electrocatalyst

ChemSusChem, Journal Year: 2024, Volume and Issue: 17(21)

Published: July 2, 2024

Abstract In the chemical industry, formaldehyde is an important bulk chemical. The traditional synthesis of involves energy intensive oxidation methanol over a metal oxide catalyst. selective electrochemical challenging. Herein, we report catalytic system with immobilized TEMPO electrode that selectively oxidizes to high turnover numbers. Upon addition various organic and inorganic bases, activity catalyst could be tuned. highest Faradaic efficiency was achieved 97.5 %, number 17100. Additionally, found rate determining step changed from in which carbonyl specie created methanol‐TEMPO adduct oxidative regeneration + species. Finally, showed applied other aliphatic alcohols.

Language: Английский

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Four-electron reduction of CO₂: from formaldehyde and acetal synthesis to complex transformations

Chemical Science, Journal Year: 2024, Volume and Issue: 15(37), P. 15023 - 15086

Published: Jan. 1, 2024

The expansive and dynamic field of the CO2 Reduction Reaction (CO2RR) seeks to harness as a sustainable carbon source or energy carrier. While significant progress has been made in two, six, eight-electron reductions CO2, four-electron reduction remains understudied. This review fills this gap, comprehensively exploring into formaldehyde (HCHO) acetal-type compounds (EOCH2OE, with E = [Si], [B], [Zr], [U], [Y], [Nb], [Ta] -R) using various CO2RR systems. These encompass (photo)electro-, bio-, thermal processes diverse reductants. Formaldehyde, versatile C1 product, is challenging synthesize isolate from CO2RR. also discusses acetal compounds, emphasizing their significance pathways distinct reactivity. Providing an overview state reduction, highlights achievements, challenges, potential produced - acetals sources for valuable product synthesis, including chiral compounds.

Language: Английский

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Electrolyte Influence on the Electrochemical Oxidation of Anhydrous Methanol to Dry Formaldehyde

Chemie Ingenieur Technik, Journal Year: 2025, Volume and Issue: unknown

Published: March 20, 2025

Abstract The electrification of the formaldehyde synthesis is investigated as a sustainable alternative to current thermal approach. formation in anhydrous methanol achieves higher Faraday efficiencies than aqueous conditions, yet operates at cell potentials. electrolyte an influential factor, and its role not understood. Here, we report on electrolyte's effect electrochemical methanol. After screening, four electrolytes were chosen for in‐depth analysis supporting ion influence. Among tested electrolytes, anion dominates conductivity viscosity while larger cations favor formaldehyde. Understanding properties crucial large‐scale industrial synthesis.

Language: Английский

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Membrane‐Free Electrocatalytic Co‐Conversions of PBS Waste Plastics and Maleic Acid into High‐Purity Succinic Acid Solid

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(44)

Published: July 27, 2024

Abstract Plastic pollution, an increasingly serious global problem, can be addressed through the full lifecycle management of plastics, including plastics recycling as one most promising approaches. System design, catalyst development, and product separation are keys in improving economics electrocatalytic recycling. Here, a membrane‐free co‐production system was devised to produce succinic acid (SA) at both anode cathode respectively by co‐electrolysis polybutylene succinate (PBS) waste biomass‐derived maleic (MA) for first time. To this end, Cr 3+ ‐Ni(OH) 2 electrocatalyst featuring much enhanced 1,4‐butanediol (BDO) oxidation reaction (BOR) activity has been synthesized role doped revealed “electron puller” accelerate rate‐determining step (RDS) Ni 2+ /Ni cycling. Impressively, extra‐high SA production rate 3.02 g h −1 ultra‐high apparent Faraday efficiency towards (FE =181.5 %) have obtained. A carbon dioxide‐assisted sequential precipitation approach developed high‐purity byproduct NaHCO 3 solids. Preliminary techno‐economic analysis demonstrates that reported is economically profitable future industrial applications.

Language: Английский

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Electrochemical CO2 Reduction to Multicarbon Products on Non‐Copper Based Catalysts

ChemSusChem, Journal Year: 2024, Volume and Issue: unknown

Published: July 10, 2024

Electrochemical CO

Language: Английский

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Advanced systems for enhanced CO₂ electroreduction

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 4, 2024

This review explores the latest developments in CO 2 electroreduction based systems, including coupling reaction co-reduction cascade and integrated capture conversion systems.

Language: Английский

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In Situ Reconstructed Hydroxyl‐Rich Atomic‐Thin Bi₂O₂CO₃ Enables Ampere‐Scale Synthesis of Formate from CO₂ with Activated Water Dissociation

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 23, 2024

Abstract Renewable electricity‐driven CO 2 electroreduction provides a promising route toward carbon neutrality and sustainable chemical production. Nevertheless, the viability of this faces constraints catalytic efficiency durability in near‐neutral electrolytes at industrial‐scale current densities, mechanistically originating from unfavorable accommodation * H species water dissociation. Herein, new strategy is reported to accelerate dissociation by rich surface hydroxyl on bismuth subcarbonate nanosheets situ electrochemical transformed hydroxide nanotube precursors. This catalyst enables electrosynthesis formate densities up 1000 mA cm −2 with >96% faradaic efficiencies flow cells, 200 h durable membrane electrode assembly dilute environment. Combined kinetic studies, characterizations, theoretical calculations reveal that atomic thickness strengthens adsorption, highly localized electron configuration, hydroxyl‐functionalized more affinitive oxygenated species, thus lowering barrier for crucial hydrogenation step proton‐coupled transfer OCHO HCOOH.

Language: Английский

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Nitrogen Bicoupled Carbon Bonding for Electrocatalysis of CO₂ and Nitrobenzene via Engineering Hydroxyl Assisted Cobalt Single Atom

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(41)

Published: July 23, 2024

Abstract The coupling of CO 2 and nitrogen‐containing species nitrobenzene has become an appealing sustainable strategy for synthesizing high‐valuable organic nitrides. However, how to realize the nitrogen bicoupled carbon bonding (C─N─C) between two been insurmountable challenge. Hydroxyl‐assisted cobalt single atom (CoN O ‐(OH) ) is engineered achieve C─N─C N, N‐dimethylaniline synthesis. adsorbed through hydroxyl groups, that can be reduced C─N with reduction intermediate on nearby Co site, vacant group continues adsorb next , which sequentially coupled coupling, achieving synthesis N‐dimethylaniline. Herein, first, achieved green via electrocatalytic in aqueous phase, a yield 505.2 µmol L −1 h CoN . In situ characterizations DFT calculations together demonstrated key *PhNCH 3 couple *CO generate *PhNCOCH much lower free energy far easier take place This work provides inspiring new insight into long‐chain

Language: Английский

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