Efficient Photoreduction of Diluted CO₂to Tunable Syngas by Ni−Co Dual Sites through d‐band Center Manipulation

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(42)

Published: Aug. 29, 2022

Photocatalytic conversion of CO2 into syngas is a promising way to address the energy and environmental challenges. Here we report integration Ni-Co dual sites on Ni doped Co3 O4 ultrathin nanosheets assembled double-hollow nanotube (Ni-Co3 NSDHN) for efficient photoreduction low-concentration . Quasi in situ spectra density functional theory calculations demonstrate that declining d-band center enables electrons accumulation dxz /dyz -2π* dz2 -5σ orbitals. As result, binding strength *CO weakened *H adsorption site modulated from metal an oxygen site. Remarkably, Ni-Co3 NSDHN exhibits superior diluted photoconversion activity controllable selectivity under irradiation visible light or even natural sunlight. A evolution rate 170.0 mmol g-1 h-1 with apparent quantum yield 3.7 % continuously adjustable CO/H2 ratios 1 : 10 are achieved.

Language: Английский

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Near-Infrared-Responsive Photocatalytic CO₂ Conversion via In Situ Generated Co₃O₄/Cu₂O

ACS Nano, Journal Year: 2023, Volume and Issue: 17(11), P. 10976 - 10986

Published: May 24, 2023

Photocatalytic CO2 conversion to fuels is a promising strategy for achieving global carbon neutrality. However, infrared light, which accounts ∼50% of the full sunlight spectrum, has not yet been effectively utilized via photocatalysis. Here, we present an approach directly power photocatalytic reduction using near-infrared light. This light-responsive process occurs on in situ generated Co3O4/Cu2O photocatalyst with nanobranch structure. Photoassisted Kelvin probe force microscopy and relative measurements demonstrate increase surface photovoltage after illumination by We also find that Cu(I) this could facilitate formation *CHO intermediate, thus enabling high-performance CH4 production yield 6.5 μmol/h selectivity 99%. Moreover, perform practically oriented direct solar-driven under concentrated achieve fuel 12.5 μmol/h.

Language: Английский

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Modular Construction of an MIL-101(Fe)@MIL-100(Fe) Dual-Compartment Nanoreactor and Its Boosted Photocatalytic Activity toward Tetracycline

ACS Applied Materials & Interfaces, Journal Year: 2022, Volume and Issue: 14(42), P. 48285 - 48295

Published: Oct. 17, 2022

Iron-based metal-organic frameworks (MOFs) have aroused extensive concern as prospective photocatalysts for antibiotic (e.g., tetracycline, TC) degradation. However, efficiencies of single and simple Fe-based MOFs still undergo restricted light absorption weak charge separation. Assembly different iron-based MOF building blocks into a hybrid MOF@MOF heterostructure reactor could be an encouraging strategy the effective capture antibiotics from aqueous phase. This paper reports new-style MIL-101(Fe)@MIL-100(Fe) photocatalyst, which was groundbreakingly constructed to realize double win boosting performances adsorption photocatalysis. The optical response range, surface open sites, separation efficiency can regulated through accurate design alteration. Attributed synergistic effects MOFs, exhibits excellent photocatalytic activity toward TC degradability compared MIL-101(Fe) MIL-100(Fe), is even superior those reported previously in literature. Furthermore, main active species •O2- h+ were proved trapping tests process. Additionally, possesses remarkable stability, maintaining more than 90% initial after fifth cycle. In brief, highly efficient Our work offers new visible-light photodegradation by exploring composite.

Language: Английский

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Modulating the Reaction Configuration by Breaking the Structural Symmetry of Active Sites for Efficient Photocatalytic Reduction of Low‐concentration CO₂

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(42)

Published: Aug. 29, 2023

Photocatalytic conversion of low-concentration CO2 is considered as a promising way to simultaneously mitigate the environmental and energy issues. However, weak adsorption tough activation process seriously compromise CO production, due chemical inertness molecule formed fragile metal-C/O bond. Herein, we designed fabricated oxygen vacancy contained Co3 O4 hollow nanoparticles on ordered macroporous N-doped carbon framework (Vo-HCo3 /OMNC) towards photoreduction . In situ spectra ab initio molecular dynamics simulations reveal that constructed able break local structural symmetry Co-O-Co sites. The formation asymmetric active site switches configuration from single-site linear model multiple-sites bending one with highly stable configuration, enhancing binding polarization molecules. As result, Vo-HCo3 /OMNC shows unprecedent activity in photocatalytic (10 % /Ar) under laboratory light source or even natural sunlight, affording syngas yield 337.8 95.2 mmol g-1 h-1 , respectively, an apparent quantum up 4.2 %.

Language: Английский

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Oxygen Vacancy‐Mediated Exciton Effect in Hierarchical BiOBr Enables Dichotomy of Energy Transfer and Electron Transfer in Photocatalysis

Advanced Functional Materials, Journal Year: 2022, Volume and Issue: 33(10)

Published: Dec. 22, 2022

Abstract Using solar energy through green and simple artificial photosynthesis systems are considered as a promising way to solve the environmental crisis. However, one of important primary steps photosynthesis, i.e., transfer, is long being ignored especially in inorganic semiconducting due small exciton binding energies. Herein, simultaneous interrogation charge transfer photoexcitation process proposed by utilizing few‐layered nanosheet‐assembled hierarchical BiOBr nanotubes with rich oxygen vacancies (OVs) efficient multifunctional photocatalysts. Benefiting from integrated 1D/2D structure abundant OV defects, excitonic effect strikes delicate balance optimized photocatalyst, showing not only improved carrier separation but also enhanced generation. As result, exhibit high efficiency toward photocatalytic CO 2 reduction an impressive evolution rate 135.6 µmol g −1 h without cocatalyst or photosensitizer. The dominant reactive species singlet ( 1 O ) discriminated for first time, which originated process, electrophilic character, whereas minor superoxide anion radical • − nucleophilic rate‐determining step aerobic oxidation sulfides.

Language: Английский

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Ni–Co Bimetallic Hydroxide Nanosheet Arrays Anchored on Graphene for Adsorption‐Induced Enhanced Photocatalytic CO₂ Reduction

Advanced Materials, Journal Year: 2022, Volume and Issue: 34(28)

Published: May 10, 2022

Photocatalytic CO2 reduction can be implemented to use , a greenhouse gas, as resource in an energy-saving and environmentally friendly way, which suitable catalytic materials are required achieve high-efficiency catalysis. Insufficient accessible active sites on the catalyst surface inhibited electron transfer severely limit photocatalytic performance. Therefore, porous aerogels constructed from composites comprising different ratios of Ni-Co bimetallic hydroxide (Nix Coy ) grown reduced graphene oxide (GR) into hierarchical nanosheet-array structure using facile situ growth method. Detailed characterization shows that this exposes numerous for enhanced adsorption-induced reduction. Moreover, under synergistic effect hydroxide, adsorption capacity well charge-carrier separation excellent. As result, Ni7 Co3 -GR exhibits highly improved performance when compared with recently reported values, high CO release rate 941.5 µmol h-1 g-1 selectivity 96.3% during . This work demonstrates new strategy designing nanocomposites abundant structures.

Language: Английский

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Band engineering of non-metal modified polymeric carbon nitride with broad spectral response for enhancing photocatalytic CO2 reduction

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 461, P. 141841 - 141841

Published: Feb. 10, 2023

Language: Английский

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Ruthenium Single Atomic Sites Surrounding the Support Pit with Exceptional Photocatalytic Activity

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)

Published: April 1, 2024

Abstract Single‐metal atomic sites and vacancies can accelerate the transfer of photogenerated electrons enhance photocatalytic performance in photocatalysis. In this study, a series nickel hydroxide nanoboards (Ni(OH) x NBs) with different loadings single‐atomic Ru ( w ‐SA‐Ru/Ni(OH) ) were synthesized via photoreduction strategy. such catalysts, are anchored to surrounding pits. Notably, SA‐Ru/Ni(OH) 0.60 wt % loading (0.60‐SA‐Ru/Ni(OH) exhibits highest catalytic (27.6 mmol g −1 h during reduction CO 2 (CO RR). Either superfluous (0.64 %, 18.9 ; 3.35 9.4 or scarce (0.06 15.8 0.29 21.95 0.58 23.4 have negative effect on its properties. Density functional theory (DFT) calculations combined experimental results revealed that be adsorbed pits; help conversion as‐adsorbed lower energy *COOH formation accelerating reaction; excessive occupy retard completion RR.

Language: Английский

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Progress in design and preparation of multi-atom catalysts for photocatalytic CO2 reduction

Science China Materials, Journal Year: 2024, Volume and Issue: 67(2), P. 397 - 423

Published: Jan. 5, 2024

Language: Английский

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Covalent Organic Framework Stabilized Single CoN4Cl2 Site Boosts Photocatalytic CO2 Reduction into Tunable Syngas

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 28, 2024

Solar carbon dioxide (CO

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