Visible-Light-Driven Highly Selective 5-Hydroxymethylfurfural Upgrading and H₂ Generation via Atomically Dispersed Ni Sites on ZnIn₂S₄ Nanosheets

ACS Catalysis, Год журнала: 2024, Номер 14(11), С. 8343 - 8352

Опубликована: Май 14, 2024

Solar-driven biomass upgrading coupled with H2 generation is promising for achieving carbon neutrality. However, identification of the active sites simultaneous photocatalytic redox reactions remains elusive at atomic level. Herein, through rational construction atomically dispersed Ni on ZnIn2S4 nanosheets (Ni1/ZIS), we decipher reactive that enable high-performance 5-hydroxymethylfurfural (HMF) oxidation evolution. Under visible-light irradiation, Ni1/ZIS greatly outperforms its pristine ZIS counterpart and can deliver high selectivity (>97%) 2,5-diformylfuran (DFF), along high-activity DFF production (394 μmol g–1 h–1) evolution (342.2 in a near stoichiometric ratio. Combined detailed experiments theoretical calculations uncover species act as HMF oxidation, while S are favored This work provides new insights into development artificial photosynthesis value-added chemicals from via sites.

Язык: Английский

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Boosting Photocatalytic Upcycling of Liquid Biomass into Biodiesel via Microenvironment Modulation

Advanced Energy Materials, Год журнала: 2024, Номер unknown

Опубликована: Авг. 13, 2024

Abstract The rational design of a photocatalyst and its microenvironmental modulation is crucial in the heterogeneous photocatalysis process, yet relevant research on photocatalytic biodiesel synthesis not explored. Herein, based prediction density functional theory (DFT) calculations, highly efficient ternary biocompatible montmorillonite (Mt) nanocomposites S‐scheme heterojunction photocatalysts (g‐C 3 N 4 ‐TiO 2 @Mt, CTM) are successfully rationally designed. By modulating microenvironment production, CTM‐2 demonstrates exceptional catalytic performance stability, achieving record‐breaking yield 98.5%. Through ex/in situ X‐ray photoelectron spectroscopy (XPS), absorption near‐edge (XANES), theoretical formation revealed, which can generate an interface electric field (IEF) that provides intrinsic driving force for carrier migration enhances surface positivity. This boosts enrichment effect electronegative oleic acid (OA) carboxyl molecules, thus greatly enriching substrate concentration improving reaction microenvironment. Moreover, fourier transform infrared spectrometer (FT‐IR)/Raman together with electron paramagnetic resonance (EPR) further confirm key intermediates CH O• ester carbonyl (C═O), DFT calculations provide reference pathway, determined to be capable significantly reducing energy barrier rate‐determining step.

Язык: Английский

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Regulating the Transfer of Photogenerated Carriers for Photocatalytic Hydrogen Evolution Coupled with Furfural Synthesis

ACS Nano, Год журнала: 2024, Номер 18(27), С. 17939 - 17949

Опубликована: Июнь 25, 2024

How to simultaneously utilize photogenerated electrons and holes still remains a critical challenge in the field of artificial photosynthesis, especially process photocatalytic hydrogen (H2) evolution coupled with biomass oxidation value-added chemicals. Herein, series-parallel photocatalyst (Cu NPs/CdS/In2O3) that can intrinsically regulate transfer carriers is ingeniously designed for H2 synergized furfural alcohol (FFA) selective (FF). Accordingly, desired FF rates near 100% selectivity toward are achieved on Cu NPs/CdS/In2O3 sealed atmospheric system. Experimental theoretical analyses confirm localized surface plasmon resonance (LSPR) effect induced by NPs accelerates reduction protons (H+) efficiently, while from In2O3 preferentially activate α-C–H bond FFA adsorbed Lewis acid sites generate FF. This work provides reference regulating synthesis.

Язык: Английский

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Electric Field Redistribution Triggered Surface Adsorption and Mass Transfer to Boost Electrocatalytic Glycerol Upgrading Coupled with Hydrogen Evolution

Advanced Energy Materials, Год журнала: 2024, Номер 14(29)

Опубликована: Май 5, 2024

Abstract Electrocatalytic glycerol oxidation reaction (GOR) stands out as an economical and prospective technology to replace oxygen evolution for co‐producing high‐valued chemicals hydrogen (H 2 ). Regulating the adsorption of (GLY) hydroxyl (OH) species is great significance improving GOR performance. Herein, a hierarchical p–n heterojunction by combining Co‐metal organic framework (MOF) nanosheets with CuO nanorod arrays (CuO@Co‐MOF) developed realize optimization on GOR. Specifically, CuO@Co‐MOF electrode exhibits superior performance conversion 98.4%, formic acid (FA) selectivity 87.3%, Faradaic efficiency (FE) 98.9%. The flow‐cell system bifunctional pairing (HER) reveals better energy efficiency. Experimental results theoretical calculations unravel redistributed electric field introducing Co‐containing that contribute improved performance, which not only enhances OH but also modulates excessive GLY CuO, thus reducing barriers FA desorption. Simultaneously, finite element analysis novelty structure can increase concentration − facilitate mass transfer in solution.

Язык: Английский

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Catalyst design and structure control for photocatalytic refineries of cellulosic biomass to fuels and chemicals

Journal of Energy Chemistry, Год журнала: 2024, Номер 94, С. 102 - 127

Опубликована: Март 9, 2024

Язык: Английский

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