Photocatalytic Production of Syngas from Biomass

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(9), P. 1057 - 1069

Published: April 12, 2023

ConspectusAs a renewable solar energy and carbon carrier, biomass exploration has received global attention. Photocatalytic valorization of into fuels chemicals is promising sustainable method for future chemical production. Photocatalysis the potential to accomplish reactions under ambient conditions due unique reaction mechanisms involving photoinduced charge carriers recently been recognized as an efficient feasible technology conversion. Biomass widely used sacrificial agent scavenge holes in photocatalytic hydrogen evolution, eventually degraded CO2 with minor amount CO. The generation CO instead more economical but also challenge photoreforming conditions.This new research direction, while until now there still lack comprehensive review article summarize provide prospects this topic. This Account will highlight our contributions direction reforming syngas (CO + H2). In 2020, we first reported conversion biopolyols sugars by employing defect-rich Cu-TiO2 nanorod photocatalyst found that formic acid key intermediate Further study revealed facet-dependent electron-trapping state on anatase TiO2 affect dehydration activity intermediates regulating electron transfer process during reaction, selective FA or from was achieved via exposing (100) (101) facets, respectively. Visible light-driven further over CdS-based photocatalyst. Sulfate modification CdS ([SO4]/CdS) constructed proton acceptor, thus efficiently facilitating proton-coupled process. Besides, put forward oxygen-controlled strategy increase rate without significant decrease selectivity controlling O2/substrate ratio. Based system, Z-scheme CdS@g-C3N4 core-shell structure CdO-CdS semicoherent interface were created facilitate enhance O2 activation, increasing rate. Moreover, developed photoelectrochemical approach separately produce H2 biomass. Nitrogen doping hexagonal WO3 nanowire array photoanode. built-in electric field generated nitrogen promoted transfer, hence improving efficiency PEC sugars. systematically analyze challenges route reforming, factors affecting give insight design systems.

Language: Английский

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Heterogeneous photocatalytic conversion of biomass to biofuels: A review

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 476, P. 146794 - 146794

Published: Oct. 20, 2023

Language: Английский

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Isolated Cu Sites in CdS Hollow Nanocubes with Doping-Location-Dependent Performance for Photocatalytic CO₂ Reduction

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(3), P. 1468 - 1479

Published: Jan. 13, 2024

Doping engineering has enabled the construction of homogeneous and abundant atomic-level catalytic sites for photocatalytic CO2 reduction with improved selectivity target product. However, little is known about effect spatial position heteroatoms on activity semiconductors toward reduction. Herein, uniform Cu doping into bulk phase hollow CdS cubes (HCC) onto surface HCC, denoted as Cu/HCC HCC@Cu, respectively, are prepared by tuning introduction order sources. Experimental analysis shows that both methods can promote separation migration photoinduced charge carriers in CdS. Notably, HCC@Cu leads to much better proton H2 production performance but lower efficiency compared bare In sharp contrast, enhances CO2-to-CO conversion while mitigating evolution. This should be ascribed smaller overpotential saturated system than Ar system. addition, atoms shifts d band center upward near Fermi energy level, which promotes adsorption activation These results indicate photoelectrons a prolonged lifetime preferably reduce molecules rather protons. The density functional theory (DFT) calculation show desorption CO*, adaptable sulfur vacancies (Vs) produced situ techniques stimulate formation CO* intermediates, resulting high CO. work reveals different heteroatom locations will provide reference design efficient photocatalysts fine structure.

Language: Английский

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D–A Conjugated Polymer/CdS S‐Scheme Heterojunction with Enhanced Interfacial Charge Transfer for Efficient Photocatalytic Hydrogen Generation

Small, Journal Year: 2024, Volume and Issue: 20(31)

Published: March 5, 2024

Abstract Owing to the improved charge separation and maximized redox capability of system, Step‐scheme (S‐scheme) heterojunctions have garnered significant research attention for efficient photocatalysis H 2 evolution. In this work, an innovative linear donor–acceptor (D–A) conjugated polymer fluorene‐alt‐(benzo‐thiophene‐dione) (PFBTD) is coupled with CdS nanosheets, forming organic–inorganic S‐scheme heterojunction. The CdS/PFBTD (CP) composite exhibits impressed hydrogen production rate 7.62 mmol g −1 h without any co‐catalysts, which ≈14 times higher than pristine CdS. It revealed that outstanding photocatalytic performance attributed formation rapid electron transfer channels through interfacial Cd─O bonding as evidenced by density functional theory (DFT) calculations in situ X‐ray photoelectron spectroscopy (XPS) analysis. mechanism involved further investigated photo‐irradiated Kelvin probe force microscopy (KPFM) This work provides a new point view on points out direction designing superior heterojunction photocatalysts.

Language: Английский

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Dual defect regulation of BiOCl halogen layer enables photocatalytic O2 activation into singlet oxygen for refractory aromatic pollutant removal

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: 345, P. 123689 - 123689

Published: Jan. 3, 2024

The generation of singlet oxygen (1O2) based on photocatalytic activation O2 is considered to have important application prospects in purifying refractory organic pollutants water. However, the uncertain dual pathway transformation activated severely limits 1O2. In this work, we show a robust BiOCl with defects (adjacent I-substitution defect and Cl vacancy) halogen layer for selective generate Combining experiments theoretical calculations, confirm that are beneficial optimizing band structures, improving carrier separation efficiency, promoting adsorption activation. More importantly, it confirmed can directionally convert into 1O2 by increasing thermodynamic conversion energy barrier non-1O2 pathways serving as necessary site functions oxidation reduction. Applying modified removal aromatic water, found has efficient stable degradation efficiency broad environmental adaptability. This work not only provides in-depth insights mechanism produce 1O2, but also lays foundation further development highly active photocatalysts remediation conversion.

Language: Английский

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Photocatalytic biomass conversion for hydrogen and renewable carbon-based chemicals

Joule, Journal Year: 2024, Volume and Issue: 8(3), P. 604 - 621

Published: Jan. 22, 2024

Language: Английский

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

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8343 - 8352

Published: May 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.

Language: Английский

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Photocatalysts for steering charge transfer and radical reactions in biorefineries

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(4), P. 438 - 451

Published: March 26, 2024

Language: Английский

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Ferrocene-boosting Zr-MOFs for efficient photocatalytic CO2 reduction: A trade-off between enhancing LMCT and frustrating Lewis acid

Chemical Engineering Journal, Journal Year: 2022, Volume and Issue: 451, P. 138747 - 138747

Published: Aug. 24, 2022

Language: Английский

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Facet-Dependent Electron Transfer Regulates Photocatalytic Valorization of Biopolyols

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(46), P. 21224 - 21231

Published: Nov. 9, 2022

The electron transfer (ET) from the conduction band of semiconductor to surface-bound species is a key step in photocatalytic reaction and strongly affects reactivity selectivity, while effect catalyst surface structure on this process has rarely been explored due lack an effective method. Herein, we have developed strategy detect measure electrons' energy adsorbates disclosed facet-dependent over anatase TiO2. photogenerated electrons are shallowly confined five-coordinated Ti atom (Ti5c) (101) facet with below 1.0 eV, deeply six-coordinated (Ti6c) subsurface (001) higher than 1.9 eV. different trap states affect ET process, thus regulating activity. Taking formic acid (FA) dehydration as probe reaction, shallow photoexcited TiO2 favors FA CO, deep makes stable. Based knowledge, successfully controlled selectivity oxidation biopolyols via selectively exposing Through controlling (001)/(101) facet, wide range can be converted into or CO up 80%. present work provides new horizon design systems.

Language: Английский

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