Atomically Local Electric Field Induced Interface Water Reorientation for Alkaline Hydrogen Evolution Reaction

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(26)

Published: March 8, 2023

The slow water dissociation process in alkaline electrolyte severely limits the kinetics of HER. orientation H2 O is well known to affect process, but hard control because its random distribution. Herein, an atomically asymmetric local electric field was designed by IrRu dizygotic single-atom sites (IrRu DSACs) tune adsorption configuration and orientation, thus optimizing process. intensity DSACs over 4.00×1010 N/C. ab initio molecular dynamics simulations combined with situ Raman spectroscopy analysis on behavior show that M-H bond length (M=active site) shortened at interface due strong gradient optimized promotes interfacial water. This work provides a new way explore role single atomic hydrogen evolution reaction.

Language: Английский

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Heteroatoms Induce Localization of the Electric Field and Promote a Wide Potential‐Window Selectivity Towards CO in the CO₂ Electroreduction

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(44)

Published: Sept. 8, 2022

Carbon dioxide electroreduction (CO2 RR) is a sustainable way of producing carbon-neutral fuels. Product selectivity in CO2 RR regulated by the adsorption energy reaction-intermediates. Here, we employ differential phase contrast-scanning transmission electron microscopy (DPC-STEM) to demonstrate that Sn heteroatoms on Ag catalyst generate very strong and atomically localized electric fields. In situ attenuated total reflection infrared spectroscopy (ATR-IR) results verified field enhances *COOH, thus favoring production CO during RR. The Ag/Sn exhibits an approximately 100 % at wide range potentials (from -0.5 -1.1 V, versus reversible hydrogen electrode), with remarkably high efficiency (EE) 76.1 %.

Language: Английский

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Nanocurvature-induced field effects enable control over the activity of single-atom electrocatalysts

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Feb. 26, 2024

Tuning interfacial electric fields provides a powerful means to control electrocatalyst activity. Importantly, can modify adsorbate binding energies based on their polarizability and dipole moment, hence operate independently of scaling relations that fundamentally limit performance. However, implementation such strategy remains challenging because typical methods the field non-uniformly affects only minority active sites. Here we discover uniformly tunable modulation be achieved using model system single-atom catalysts (SACs). These consist M-N

Language: Английский

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Electronic Structure Design of Transition Metal-Based Catalysts for Electrochemical Carbon Dioxide Reduction

ACS Nano, Journal Year: 2024, Volume and Issue: 18(14), P. 9823 - 9851

Published: March 28, 2024

With the increasingly serious greenhouse effect, electrochemical carbon dioxide reduction reaction (CO2RR) has garnered widespread attention as it is capable of leveraging renewable energy to convert CO2 into value-added chemicals and fuels. However, performance CO2RR can hardly meet expectations because diverse intermediates complicated processes, necessitating exploitation highly efficient catalysts. In recent years, with advanced characterization technologies theoretical simulations, exploration catalytic mechanisms gradually deepened electronic structure catalysts their interactions intermediates, which serve a bridge facilitate deeper comprehension structure-performance relationships. Transition metal-based (TMCs), extensively applied in CO2RR, demonstrate substantial potential for further modulation, given abundance d electrons. Herein, we discuss representative feasible strategies modulate catalysts, including doping, vacancy, alloying, heterostructure, strain, phase engineering. These approaches profoundly alter inherent properties TMCs interaction thereby greatly affecting rate pathway CO2RR. It believed that rational design modulation fundamentally provide viable directions development toward conversion many other small molecules.

Language: Английский

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Twin Heterostructure Engineering and Facet Effect Boosts Efficient Reduction CO₂-to-Ethanol at Low Potential on Cu₂O@Cu₂S Catalysts

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(5), P. 3266 - 3277

Published: Feb. 15, 2024

Copper oxide (Cu2O) is considered a promising catalyst that can effectively reduce the overpotential of CO2 reduction reaction (CO2 RR) and increase selectivity for C2+ products. However, developing high-performance stable CO2-to-ethanol (C2H5OH) based-Cu2O electrocatalysts remains challenging. In this work, Cu2O@Cu2S twin heterojunction catalysts with multitwin boundaries are designed to afford C2H5OH productivity at low potential through electrocatalytic RR, highly dependent on facet nanocubes outperforming octahedra. Detailed electrochemical experiments, density functional theory (DFT) calculations in situ infrared spectroscopy reveals introduction Cu2S boosts high coverage *CO, which easily spillover generate *CHOH_*CO coupling pathway. A production begins an ultralow −0.45 V vs RHE reaches 34 43.9% Faradaic efficiencies (FE) −0.65 H-cell flow cell, respectively. Meanwhile, constructed interface coherent structure suitable band facilitate electron transfer from Cu2O Cu2S, leading stability Cu+ valence states. This work provides avenue precisely design by regulating configuration.

Language: Английский

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Challenges and opportunities of atomic-scales reactive sites in thriving electrochemical CO2 reduction reaction

Nano Today, Journal Year: 2024, Volume and Issue: 55, P. 102152 - 102152

Published: Jan. 13, 2024

Language: Английский

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(111) Facet‐oriented Cu₂Mg Intermetallic Compound with Cu₃‐Mg Sites for CO₂ Electroreduction to Ethanol with Industrial Current Density

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(17)

Published: March 4, 2024

Abstract The efficient ethanol electrosynthesis from CO 2 is challenging with low selectivity at high electrolysis rates, due to the competition H and other reduction products. Copper‐based bimetallic electrocatalysts are potential candidates for ‐to‐ethanol conversion, but secondary metal has mainly been focused on active components (such as Ag, Sn) electroreduction, which also promote of ethylene or products rather than ethanol. Limited attention given alkali‐earth metals their inherently chemical property. Herein, we rationally synthesized a (111) facet‐oriented nano Cu Mg (designated Mg(111)) intermetallic compound high‐density ordered 3 ‐Mg sites. in situ Raman spectroscopy density function theory calculations revealed that − + sites allowed increase *CO surface coverage, decrease reaction energy *CO−CO coupling, stabilize *CHCHOH intermediates, thus promoting formation pathway. Mg(111) catalyst exhibited FE C2H5OH 76.2±4.8 % 600 mA⋅cm −2 , peak value | j 720±34 almost 4 times using conventional (311) facets, comparable best reported values electroreduction.

Language: Английский

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Mechanism of Key Intermediates Regulation in Electrocatalytic Nitrate-to-Ammonia Conversion Driven by Polarized Electric Field

Nano Energy, Journal Year: 2025, Volume and Issue: unknown, P. 110708 - 110708

Published: Jan. 1, 2025

Language: Английский

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High-Throughput Computational Screening of Metal–Organic Frameworks as High-Performance Electrocatalysts for CO₂RR

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(24), P. 15271 - 15281

Published: Nov. 29, 2022

Metal–organic frameworks (MOFs) are considered as promising electrocatalytic materials for the carbon dioxide reduction reaction (CO2RR) due to their various excellent properties. Here, through multistep high-throughput screening of Computation-Ready, Experimental (CoRE) MOF database, including structural rationality check, pore size screening, adsorption capacity prediction, open metal site identification, CO2 molecular activation capacity, and path calculation, MOFs named GAFRUD, CAJQEL, cg400449c identified potential catalysts CO2RR. Furthermore, based on density functional theory calculations, we propose that polarity coordination bonds between atoms in ligands has a significant impact molecules, selectivity HCOOH mainly depends energy difference *HCOO *COOH. This principle is further validated by experimental results, which will provide guidelines rational design MOF-based electrocatalysts

Language: Английский

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Various carbon-based MgAl2O4 adsorbents and their removal efficiency of CR dye and antibiotics in aqueous media: High selective adsorption capacity, performance prediction and mechanism insight

Ceramics International, Journal Year: 2023, Volume and Issue: 49(16), P. 26734 - 26746

Published: May 23, 2023

Language: Английский

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