Surface Modification of 2D Photocatalysts for Solar Energy Conversion

Advanced Materials, Год журнала: 2022, Номер 34(23)

Опубликована: Март 9, 2022

Abstract 2D materials show many particular properties, such as high surface‐to‐volume ratio, anisotropic degree, and adjustable chemical functionality. These unique properties in have sparked immense interest due to their applications photocatalytic systems, resulting significantly enhanced light capture, charge‐transfer kinetics, surface reaction. Herein, the research progress photocatalysts based on varied compositions functions, followed by specific modification strategies, is introduced. Fundamental principles focusing harvesting, charge separation, molecular adsorption/activation 2D‐material‐based system are systemically explored. The examples described here detail use of various energy‐conversion including water splitting, carbon dioxide reduction, nitrogen fixation, hydrogen peroxide production, organic synthesis. Finally, elaborating challenges possible solutions for developing these materials, review expected provide some inspiration future used efficient energy conversions.

Язык: Английский

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Electrocatalytic CO₂-to-C₂₊ with Ampere-Level Current on Heteroatom-Engineered Copper via Tuning *CO Intermediate Coverage

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(32), С. 14936 - 14944

Опубликована: Авг. 4, 2022

An ampere-level current density of CO2 electrolysis is critical to realize the industrial production multicarbon (C2+) fuels. However, under such a large density, poor CO intermediate (*CO) coverage on catalyst surface induces competitive hydrogen evolution reaction, which hinders reduction reaction (CO2RR). Herein, we report reliable CO2-to-C2+ by heteroatom engineering Cu catalysts. The Cu-based compounds with (N, P, S, O) are electrochemically reduced heteroatom-derived significant structural reconstruction CO2RR conditions. It found that N-engineered (N-Cu) exhibits best productivity remarkable Faradaic efficiency 73.7% -1100 mA cm-2 and an energy 37.2% -900 cm-2. Particularly, it achieves C2+ partial -909 at -1.15 V versus reversible electrode, outperforms most reported In situ spectroscopy indicates adjusts *CO adsorption alters local H proton consumption in solution. Density functional theory studies confirm high strength N-Cu results from depressed HER promoted both bridge atop sites Cu, greatly reduces barrier for C-C coupling.

Язык: Английский

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Porphyrin-based framework materials for energy conversion

Deleted Journal, Год журнала: 2022, Номер 1, С. e9120009 - e9120009

Опубликована: Май 26, 2022

With the increasing demand for fuel causing serious environmental pollution, it is urgent to develop new and environmentally friendly energy conversion devices. These devices, however, require good, inexpensive materials electrodes so on. The multifunctional properties of porphyrins enable framework (e.g., metal-organic frameworks covalent organic frameworks) be applied in devices due their simple synthesis, high chemical stability, abundant metallic active sites, adjustable crystalline structure specific surface area. Herein, types porphyrin structural blocks are briefly reviewed. They can used as ligands or directly assembled with generate high-performance electro-/photo-catalysts. catalysts electro-/photo-catalytic water splitting, carbon dioxide reduction, electrocatalytic oxygen reduction also summarized introduced. At end article, we present challenges porphyrin-based above application corresponding solutions. We expect flourish coming years.

Язык: Английский

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Dynamic Reconstitution Between Copper Single Atoms and Clusters for Electrocatalytic Urea Synthesis

Advanced Materials, Год журнала: 2023, Номер 35(18)

Опубликована: Фев. 6, 2023

Electrocatalytic CN coupling between carbon dioxide and nitrate has emerged to meet the comprehensive demands of footprint closing, valorization waste, sustainable manufacture urea. However, identification catalytic active sites design efficient electrocatalysts remain a challenge. Herein, synthesis urea catalyzed by copper single atoms decorated on CeO2 support (denoted as Cu1 -CeO2 ) is reported. The catalyst exhibits an average yield rate 52.84 mmol h-1 gcat.-1 at -1.6 V versus reversible hydrogen electrode. Operando X-ray absorption spectra demonstrate reconstitution (Cu1 clusters (Cu4 during electrolysis. These electrochemically reconstituted Cu4 are real for electrocatalytic synthesis. Favorable reactions formation validated using operando synchrotron-radiation Fourier transform infrared spectroscopy theoretical calculations. Dynamic transformations single-atom configurations occur when applied potential switched open-circuit potential, endowing with superior structural electrochemical stabilities.

Язык: Английский

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Cu-Zn-based alloy/oxide interfaces for enhanced electroreduction of CO2 to C2+ products

Journal of Energy Chemistry, Год журнала: 2023, Номер 83, С. 90 - 97

Опубликована: Май 11, 2023

Язык: Английский

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Modulation of *CH_xO Adsorption to Facilitate Electrocatalytic Reduction of CO₂ to CH₄ over Cu-Based Catalysts

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(12), С. 6622 - 6627

Опубликована: Март 20, 2023

Copper (Cu) can efficiently catalyze the electrochemical CO2 reduction reaction (CO2RR) to produce value-added fuels and chemicals, among which methane (CH4) has drawn attention due its high mass energy density. However, linear scaling relationship between adsorption energies of *CO *CHxO on Cu restricts selectivity toward CH4. Alloying a secondary metal in provides new freedom break relationship, thus regulating product distribution. This paper describes controllable electrodeposition approach alloying with oxophilic (M) steer pathway The optimized La5Cu95 electrocatalyst exhibits CH4 Faradaic efficiency 64.5%, partial current density 193.5 mA cm-2. introduction La could lower barrier for hydrogenation by strengthening M-O bond, would also promote breakage C-O bond *CH3O formation work avenue design Cu-based electrocatalysts achieve CO2RR through modulation behaviors key intermediates.

Язык: Английский

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Stabilizing Copper by a Reconstruction-Resistant Atomic Cu–O–Si Interface for Electrochemical CO₂ Reduction

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(15), С. 8656 - 8664

Опубликована: Апрель 8, 2023

Copper (Cu), a promising catalyst for electrochemical CO2 reduction (CO2R) to multi-electron products, suffers from an unavoidable and uncontrollable reconstruction process during the reaction, which not only may lead deactivation but also brings great challenges exploration of structure-performance relationship. Herein, we present efficient strategy stabilizing Cu with silica synthesize reconstruction-resistant CuSiOx amorphous nanotube catalysts abundant atomic Cu-O-Si interfacial sites. The strong interaction between makes sites ultrastable in CO2R reaction without any apparent reconstruction, thus exhibiting high CO2-to-CH4 selectivity (72.5%) stability (FECH4 remains above 60% after 12 h test). A remarkable conversion rate 0.22 μmol cm-2 s-1 was achieved flow cell device. This work provides very route design highly active stable Cu-based catalysts.

Язык: Английский

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Carbon‐Confined Indium Oxides for Efficient Carbon Dioxide Reduction in a Solid‐State Electrolyte Flow Cell

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(21)

Опубликована: Март 8, 2022

Developing robust electrocatalysts and advanced devices is important for electrochemical carbon dioxide (CO2 ) reduction toward the generation of valuable chemicals. We present herein a carbon-confined indium oxide electrocatalyst stable efficient CO2 reduction. The reductive corrosion oxidative to metallic state during electrolysis could be prevented by protection, applied layer also optimizes reaction intermediate adsorption, which enables both high selectivity activity In liquid-phase flow cell, formate exceeds 90 % in wide potential window from -0.8 V -1.3 vs. RHE. continuous production ca. 0.12 M pure formic acid solution further demonstrated at current density 30 mA cm-2 solid-state electrolyte mediated reactor. This work provides significant concepts parallel development carbon-neutral technologies.

Язык: Английский

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In Situ Reconstruction of Cu–N Coordinated MOFs to Generate Dispersive Cu/Cu₂O Nanoclusters for Selective Electroreduction of CO₂to C₂H₄

ACS Catalysis, Год журнала: 2022, Номер 12(24), С. 15230 - 15240

Опубликована: Ноя. 29, 2022

Electrochemical reduction of CO2 to obtain high-value-added feedstocks is a promising strategy alleviate the energy crisis. Cu-based catalysts generate multi-carbon products with high activity in reaction (CO2RR), although great challenges remain selectivity and stability catalysts. Here, highly active Cu/Cu2O nanoclusters were produced via situ electrochemical reconstruction using Cu–N coordinated MOFs as precursors for selective C2H4 synthesis, showing Faradaic efficiency 70.2 ± 1.7% toward partial current density 12.38 mA·cm–2 at −1.03 V vs RHE CO2RR. In infrared spectroscopy observation *CO*CO *CO*COH intermediates confirmed formation pathway, while Raman spectroscopy, ex XPS, HRTEM evidenced that coexisting Cu2O Cu sites. The method could be used synthesize electroreduction.

Язык: Английский

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Electron‐Rich Bi Nanosheets Promote CO₂⋅⁻ Formation for High‐Performance and pH‐Universal Electrocatalytic CO₂ Reduction

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(11)

Опубликована: Янв. 20, 2023

Electrochemical CO2 reduction reaction (CO2 RR) to chemical fuels such as formate offers a promising pathway carbon-neutral future, but its practical application is largely inhibited by the lack of effective activation molecules and pH-universal feasibility. Here, we report an electronic structure manipulation strategy electron-rich Bi nanosheets, where electrons transfer from Cu donor acceptor in bimetallic Cu-Bi, enabling RR towards with concurrent high activity, selectivity stability (acidic, neutral alkaline) electrolytes. Combined situ Raman spectra computational calculations unravel that promotes ⋅- formation activate molecules, enhance adsorption strength *OCHO intermediate up-shifted p-band center, thus leading superior activity formate. Further integration robust nanosheets into III-V-based photovoltaic solar cell results unassisted artificial leaf solar-to-formate (STF) efficiency 13.7 %.

Язык: Английский

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