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

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(32), P. 14936 - 14944

Published: Aug. 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.

Language: Английский

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S-scheme MIL-101(Fe) octahedrons modified Bi2WO6 microspheres for photocatalytic decontamination of Cr(VI) and tetracycline hydrochloride: Synergistic insights, reaction pathways, and toxicity analysis

Chemical Engineering Journal, Journal Year: 2022, Volume and Issue: 455, P. 140943 - 140943

Published: Dec. 14, 2022

Language: Английский

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Porphyrin-based framework materials for energy conversion

Deleted Journal, Journal Year: 2022, Volume and Issue: 1, P. e9120009 - e9120009

Published: May 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.

Language: Английский

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Interfacial polarization in metal-organic framework reconstructed Cu/Pd/CuOx multi-phase heterostructures for electrocatalytic nitrate reduction to ammonia

Applied Catalysis B Environment and Energy, Journal Year: 2022, Volume and Issue: 318, P. 121805 - 121805

Published: July 28, 2022

Language: Английский

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Designing Electrophilic and Nucleophilic Dual Centers in the ReS₂ Plane toward Efficient Bifunctional Catalysts for Li-CO₂ Batteries

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(7), P. 3106 - 3116

Published: Feb. 11, 2022

Two-dimensional transition metal dichalcogenides (TMDCs) show great potential as efficient catalysts for Li-CO2 batteries. However, the basal plane engineering on TMDCs toward bifunctional batteries is still poorly understood. In this work, density functional theory calculations reveal that nucleophilic N dopants and electrophilic S vacancies in ReS2 tailor interactions with Li atoms C/O intermediates, respectively. The dual centers suitable adsorption all intermediates during discharge charge, resulting a small energy barrier rate-determining step. Thus, an catalyst produced As result, optimal achieves ultrasmall voltage gap of 0.66 V ultrahigh efficiency 81.1% at 20 μA cm-2, which superior to those previous under similar conditions. introduction provides new avenues designing excellent

Language: Английский

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Boosting Energy Efficiency and Stability of Li–CO₂ Batteries via Synergy between Ru Atom Clusters and Single‐Atom Ru–N₄ sites in the Electrocatalyst Cathode

Advanced Materials, Journal Year: 2022, Volume and Issue: 34(17)

Published: March 1, 2022

The Li-CO2 battery is a novel strategy for CO2 capture and energy-storage applications. However, the sluggish reduction evolution reactions cause large overpotential poor cycling performance. Herein, new catalyst containing well-defined ruthenium (Ru) atomic clusters (RuAC ) single-atom Ru-N4 (RuSA composite sites on carbon nanobox substrate (RuAC+SA @NCB) (NCB = nitrogen-doped nanobox) fabricated by utilizing different complexation effects between Ru cation amine group (NH2 quantum dots or nitrogen moieties NCB. Systematic experimental theoretical investigations demonstrate vital role of electronic synergy RuAC in improving electrocatalytic activity toward reaction (CO2 ER) RR). properties are essentially modulated adjacent species, which optimizes interactions with key intermediates thereby reducing energy barriers rate-determining steps RR ER. Remarkably, RuAC+SA @NCB-based cell displays unprecedented overpotentials as low 1.65 1.86 V at ultrahigh rates 1 2 A g-1 , twofold lifespan than baselines. findings provide to construct catalysts active comprising multiple atom assemblies high-performance metal-CO2 batteries.

Language: Английский

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Halide-guided active site exposure in bismuth electrocatalysts for selective CO2 conversion into formic acid

Nature Catalysis, Journal Year: 2023, Volume and Issue: 6(9), P. 796 - 806

Published: Aug. 17, 2023

Abstract It remains a challenge to identify the active sites of bismuth catalysts in electrochemical CO 2 reduction reaction. Here we show through situ characterization that activation oxyhalide electrocatalysts metallic is guided by halides. In X-ray diffraction results bromide promotes selective exposure planar surfaces, whereas chloride and iodide result more disordered sites. Furthermore, find bromide-activated outperform counterparts, achieving high current density (>100 mA cm –2 ) formic acid selectivity (>90%), suggesting surfaces are for addition, absorption spectroscopy measurements reveal reconstruction proceeds rapidly chloride-activated gradually when present, facilitating formation ordered surfaces. These findings pivotal role halogens on facet activated bismuth-based during

Language: Английский

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Inter‐Metal Interaction with a Threshold Effect in NiCu Dual‐Atom Catalysts for CO₂ Electroreduction

Advanced Materials, Journal Year: 2022, Volume and Issue: 35(11)

Published: Nov. 26, 2022

Dual-atom catalysts (DACs) have become an emerging platform to provide more flexible active sites for electrocatalytic reactions with multi-electron/proton transfer, such as the CO2 reduction reaction (CRR). However, introduction of asymmetric dual-atom causes complexity in structure, leaving incomprehensive understanding inter-metal interaction and catalytic mechanism. Taking NiCu DACs example, herein, a rational structural model is proposed, distance-dependent investigated by combining theoretical simulations experiments, including density functional theory computation, aberration-corrected transmission electron microscopy, synchrotron-based X-ray absorption fine Monte Carlo experiments. A distance threshold around 5.3 Å between adjacent NiN4 CuN4 moieties revealed trigger effective electronic regulation boost CRR performance on both selectivity activity. universal macro-descriptor rigorously correlating intrinsic material features (e.g., metal loading thickness) established guide design synthesis advanced DACs. This study highlights significance identifying DACs, helps bridge gap experimental atomically dispersed highly correlated sites.

Language: Английский

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Au-activated N motifs in non-coherent cupric porphyrin metal organic frameworks for promoting and stabilizing ethylene production

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Jan. 17, 2022

Abstract Direct implementation of metal-organic frameworks as the catalyst for CO 2 electroreduction has been challenging due to issues such poor conductivity, stability, and limited > 2e − products. In this study, Au nanoneedles are impregnated into a cupric porphyrin-based framework by exploiting ligand carboxylates 3+ -reducing agent, simultaneously cleaving ligand-node linkage. Surprisingly, despite lack coherent structure, Au-inserted affords superb ethylene selectivity up 52.5% in Faradaic efficiency, ranking among best reported literature. Through operando X-ray, infrared spectroscopies density functional theory calculations, enhanced is attributed Au-activated nitrogen motifs coordination with Cu centers C-C coupling at metalloporphyrin sites. Furthermore, demonstrates both improved structural catalytic ascribed altered charge conduction path that bypasses incoherent framework. This study underlines modulation reticular structure metal impregnation steering reduction reaction pathway.

Language: Английский

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A Nanocomposite of Bismuth Clusters and Bi₂O₂CO₃ Sheets for Highly Efficient Electrocatalytic Reduction of CO₂ to Formate

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(3)

Published: Oct. 29, 2022

The renewable-electricity-driven CO2 reduction to formic acid would contribute establishing a carbon-neutral society. current catalyst suffers from limited activity and stability under high selectivity the ambiguous nature of active sites. Herein, we report powerful Bi2 S3 -derived that demonstrates density 2.0 A cm-2 with formate Faradaic efficiency 93 % at -0.95 V versus reversible hydrogen electrode. energy conversion single-pass yield reach 80 67 %, respectively, durability reaches 100 h an industrial-relevant density. Pure concentration 3.5 mol L-1 has been produced continuously. Our operando spectroscopic theoretical studies reveal dynamic evolution into nanocomposite composed Bi0 clusters O2 CO3 nanosheets pivotal role -Bi2 interface in activation conversion.

Language: Английский

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