Stabilizing Cu²⁺ Ions by Solid Solutions to Promote CO₂ Electroreduction to Methane

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(5), P. 2079 - 2084

Published: Jan. 28, 2022

Copper is the only metal catalyst that can perform electrocatalytic CO2 reduction reaction (CRR) to produce hydrocarbons and oxygenates. Its surface oxidation state determines pathway various products. However, under cathodic potential of CRR conditions, chemical composition most Cu-based catalysts inevitably undergoes electroreduction from Cu2+ Cu0 or Cu1+ species, which generally coupled with phase reconstruction formation new active sites. Since initial sites are hard retain, there have been few studies about for CRR. Herein we propose a solid-solution strategy stabilize ions by incorporating them into CeO2 matrix, works as self-sacrificing ingredient protect species. In situ spectroscopic characterization density functional theory calculations reveal compared conventionally derived Cu sites, species in solid solution (Cu-Ce-Ox) significantly strengthen adsorption *CO intermediate, facilitating its further hydrogenation CH4 instead dimerization give C2 As result, different other catalysts, Cu-Ce-Ox delivered high Faradaic efficiency 67.8% low value 3.6% C2H4.

Language: Английский

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Atomically Dispersed Indium‐Copper Dual‐Metal Active Sites Promoting C−C Coupling for CO₂ Photoreduction to Ethanol

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(40)

Published: Aug. 10, 2022

Photoreduction of CO2 to C2+ solar fuel is a promising carbon-neutral technology for renewable energy. This strategy challenged by its low productivity due efficiency in multielectron utilization and slow C-C coupling kinetics. work reports dual-metal photocatalyst consisting atomically dispersed indium copper anchored on polymeric carbon nitride (InCu/PCN), which the photoreduction delivered an excellent ethanol production rate 28.5 μmol g-1 h-1 with high selectivity 92 %. Coupled experimental investigation DFT calculations reveal following mechanisms underpinning performance this catalyst. Essentially, In-Cu interaction enhances charge separation accelerating transfer from PCN metal sites. Indium also transfers electrons neighboring via Cu-N-In bridges, increasing electron density active Furthermore, sites promote adsorption *CO intermediates lower energy barrier coupling.

Language: Английский

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

Journal of Energy Chemistry, Journal Year: 2023, Volume and Issue: 83, P. 90 - 97

Published: May 11, 2023

Language: Английский

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Tailoring the Surface and Interface Structures of Copper‐Based Catalysts for Electrochemical Reduction of CO₂ to Ethylene and Ethanol

Small, Journal Year: 2022, Volume and Issue: 18(18)

Published: Feb. 7, 2022

Abstract Electrochemical CO 2 reduction to valuable ethylene and ethanol offers a promising strategy lower emissions while storing renewable electricity. Cu‐based catalysts have shown the potential for ‐to‐ethylene/ethanol conversion, but still suffer from low activity selectivity. Herein, effects of surface interface structures in production are systematically discussed. Both reactions involve three crucial steps: formation intermediate, CC coupling, hydrodeoxygenation C intermediates. For ethylene, key step is which can be enhanced by tailoring catalyst such as sites on facets, Cu 0 /Cu δ+ species nanopores, well optimized molecule–catalyst electrolyte–catalyst interfaces further promoting higher production. While controllable intermediate important ethanol, achieved tuning stability oxygenate intermediates through metallic cluster induced special atomic configuration bimetallic synergy double active surface. Additionally, constraining coverage complex–catalyst stabilizing CO bond N‐doped carbon/Cu also enhance The structure–performance relationships will provide guidance design highly efficient .

Language: Английский

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Imparting CO₂ Electroreduction Auxiliary for Integrated Morphology Tuning and Performance Boosting in a Porphyrin‐based Covalent Organic Framework

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 61(5)

Published: Nov. 22, 2021

Strategies that enable simultaneous morphology-tuning and electroreduction performance boosting are much desired for the exploration of covalent organic frameworks in efficient CO2 electroreduction. Herein, a kind functionalizing exfoliation agent has been selected to simultaneously modify exfoliate bulk COFs into functional nanosheets investigate their performance. The obtained (Cu-Tph-COF-Dct) with large-scale (≈1.0 μm) ultrathin (≈3.8 nm) morphology superior FECH4 (≈80 %) (almost doubly enhanced than bare COF) large current-density (-220.0 mA cm-2 ) at -0.9 V. boosted can be ascribed immobilized (Dct groups) integrated amino triazine groups strengthen absorption/activation, stabilize intermediates enrich CO concentration around Cu active sites as revealed by DFT calculations. point-to-point functionalization strategy modularly assembling Dct-functionalized COF catalyst will open up attractive possibility developing RR electrocatalysts.

Language: Английский

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Microscopic-Level Insights into the Mechanism of Enhanced NH₃ Synthesis in Plasma-Enabled Cascade N₂ Oxidation–Electroreduction System

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(23), P. 10193 - 10200

Published: May 19, 2022

Integrated/cascade plasma-enabled N2 oxidation and electrocatalytic NOx– (where x = 2, 3) reduction reaction (pNOR-eNOx–RR) holds great promise for the renewable synthesis of ammonia (NH3). However, corresponding activated effects process plasma toward O2 molecules mechanism eNOx–RR to NH3 are unclear need be further uncovered, which largely limits large-scale deployment this integration technology. Herein, we systematically investigate activation recombination processes molecules, more meaningfully, at a microscopic level is also decoupled using copper (Cu) nanoparticles as representative electrocatalyst. The concentration produced NOx in pNOR system confirmed function length spark discharge well volumetric ratio feeding gas. successive protonation key N-containing intermediates (e.g., −NH2) detected with situ infrared spectroscopy. Besides, Raman spectroscopy reveals dynamic reconstruction Cu during process. nanoparticle-driven pNOR-eNOx–RR can finally achieve high yield rate ∼40 nmol s–1 cm–2 Faradaic efficiency nearly 90%, overperforming benchmarks reported literature. It anticipated that work will stimulate practical development green electrosynthesis directly from air water under ambient conditions.

Language: Английский

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Stabilization of Cu⁺ via Strong Electronic Interaction for Selective and Stable CO₂ Electroreduction

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(31)

Published: May 31, 2022

Copper oxide-based materials effectively electrocatalyze carbon dioxide reduction (CO2 RR). To comprehend their role and achieve high CO2 RR activity, Cu+ in copper oxides must be stabilized. As an electrocatalyst, Cu2 O nanoparticles were decorated with hexagonal boron nitride (h-BN) nanosheets to stabilize . The C2 H4 /CO ratio increased 1.62-fold the O-BN compared that O. Experimental theoretical studies confirmed strong electronic interactions between two components O-BN, which strengthens Cu-O bonds. Electrophilic h-BN receives partial electron density from O, protecting bonds attack during stabilizing species long-term electrolysis. well-retained enhanced product selectivity improved stability of O-BN. This work offers new insight into metal-valence-state-dependent catalysts, enabling design advanced catalysts.

Language: Английский

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The Crystal Plane is not the Key Factor for CO₂‐to‐Methane Electrosynthesis on Reconstructed Cu₂O Microparticles

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 61(7)

Published: Dec. 9, 2021

Cu2 O microparticles with controllable crystal planes and relatively high stability have been recognized as a good platform to understand the mechanism of electrocatalytic CO2 reduction reaction (CO2 RR). Herein, we demonstrate that in situ generated O/Cu interface plays key role determining selectivity methane formation, rather than initial plane reconstructed microparticles. Experimental results indicate evolution is dominated on all three different similar Tafel slopes long-term stabilities. Density functional theory (DFT) calculations further reveal *CO protonated via bridge configuration at interface, regardless O. The Gibbs free energy changes (ΔG) *CHO are close more negative *OCCOH, indicating formation favorable ethylene planes.

Language: Английский

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Organic Additive‐derived Films on Cu Electrodes Promote Electrochemical CO₂ Reduction to C₂₊ Products Under Strongly Acidic Conditions

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(12)

Published: Jan. 19, 2023

Abstract Electrochemical CO 2 reduction (CO R) at low pH is desired for high utilization; the competing hydrogen evolution reaction (HER) remains a challenge. High alkali cation concentration operating current density has recently been used to promote electrochemical R pH. Herein we report an alternative approach selective (>70 % Faradaic efficiency C 2+ products, FE C2+ ) (pH 2; H 3 PO 4 /KH and potassium ([K + ]=0.1 M) using organic film‐modified polycrystalline copper (Modified‐Cu). Such electrode effectively mitigates HER due attenuated proton transport. Modified‐Cu still achieves (45 with Cu foil /55 GDE) under 1.0 M (pH≈1) [K ] (0.1 M), even current, conditions where can otherwise dominate.

Language: Английский

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Over 70 % Faradaic Efficiency for CO₂ Electroreduction to Ethanol Enabled by Potassium Dopant‐Tuned Interaction between Copper Sites and Intermediates

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(36)

Published: July 14, 2022

It is highly desired yet challenging to steer the CO2 electroreduction reaction (CO2 ER) toward ethanol with high selectivity, for which evolution of intermediates on catalytically active sites holds key. Herein, we report that K doping in Cu2 Se nanosheets array Cu foam serves as a versatile way tune interaction between and ER, enabling selective production ethanol. As revealed by characterization simulation, electron transfer from can stabilize CuI species facilitate adsorption linear *COL bridge *COB promote C-C coupling during ER. result, optimized K11.2% -Cu2 catalyze ER single liquid product selectivity potential area -0.6 -1.2 V. Notably, it offers Faradaic efficiency 70.3 % at -0.8 V stable 130 h.

Language: Английский

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