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化学进展 ›› :0- DOI: 10.7536/PC20260401
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基于内建电场的工程化设计实现高效二氧化碳还原：基础与展望

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摘要

二氧化碳电化学还原（CO2RR）是闭合全球碳循环的关键技术，但其工业转化受到反应动力学缓慢、多碳选择性差以及与析氢反应的激烈竞争等根本性限制。近年来，电催化剂的设计模式已从本体材料优化转向精确的原子级微环境调控，而这一转变的核心在于内建电场的构建。本文系统地探讨内建电场的物理起源和催化机制，阐明高度局域化的内部静电场如何将催化剂微环境与宏观外加电势解耦。内建电场通过与关键中间体的偶极矩相互作用，从热力学上降低初始CO2活化的活化能垒，并策略性地稳定极性*OCCO过渡态，从而引导C-C偶联。此外，内建电场还能通过静电排斥双电层中的质子，从本质上抑制竞争反应。本文全面总结了用于诱导强烈表面电荷不对称性的先进合成策略，包括异质结构建、缺陷工程和动态铁电调制，并且重点分析目前仍存在的结构和理论瓶颈。

Abstract

The electrochemical reduction of carbon dioxide (CO2RR) is a critical technology for closing the global carbon cycle, yet its industrial translation is fundamentally limited by sluggish kinetics, poor multicarbon selectivity, and fierce competition from the hydrogen evolution reaction. Recently, the model of electrocatalyst design has shifted from bulk material optimization to precise atomic-level microenvironment modulation. At the forefront of this shift is the engineering of built-in electric fields (BIEFs). This review systematically examines the physical origins and catalytic mechanisms of BIEFs, elucidating how highly localized, internal electrostatic fields decouple the catalyst microenvironment from macroscopic applied potentials. By interacting with the dipole moments of key intermediates, BIEFs thermodynamically lower activation barriers for initial CO2 activation and strategically stabilize the polar *OCCO transition state, thereby directing C-C coupling. Furthermore, BIEFs intrinsically suppress the competing reaction by electrostatically repelling protons from the electrical double layer. We comprehensively summarize state-of-the-art synthetic strategies, including heterojunction construction, defect engineering, and dynamic ferroelectric modulation, used to induce intense surface charge asymmetry. Finally, we conclude by critically outlining the remaining structural and theoretical bottlenecks, providing a roadmap for scaling BIEF-engineered catalysts via advanced modeling and machine learning toward industrial membrane electrode assemblies.

关键词

二氧化碳还原 / 内建电场 / CO2活化 / 微环境策略 / 异质结接触

Key words

electrochemical CO2 reduction / built-in electric fields / CO2 activation / microenvironment strategies / heterojunction contact.

引用本文

引用格式 ▾
郑星群, 梁馨月, 华青松. 基于内建电场的工程化设计实现高效二氧化碳还原：基础与展望[J]. 化学进展, , (): 0 DOI:10.7536/PC20260401
Xingqun Zheng, Xinyue Liang, Qingsong Hua. Progress in Chemistry 0 DOI:10.7536/PC20260401

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