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    低体积分数CO2转化电催化剂设计研究进展

    Research progress on electrocatalyst design for low-concentration CO2 conversion

    • 摘要: “双碳”目标的实现迫切需要高效的碳减排与资源化技术,而二氧化碳(CO2)电催化还原技术因反应条件温和、反应参数易外部调控、易与可再生能源结合等众多优势成为关键路径之一。然而,当前大多数研究集中于高纯度CO2的转化,而全球CO2排放的主要来源(如燃煤电厂烟气CO2体积分数仅约15%)和大气环境(CO2体积分数约0.04%)中低体积分数CO2的直接转化仍面临严峻挑战。这些挑战主要包括反应物物质的量浓度低导致的严重传质限制、反应动力学速率缓慢、产物选择性低等,亟待通过电催化剂设计突破技术瓶颈。在简要介绍eCO2RR机理的基础上,具体分析了电催化低体积分数CO2还原的制约因素,进而系统综述了面向低体积分数CO2转化的电催化剂设计策略,揭示了从微观结构到宏观性能的调控逻辑,旨在为高效催化体系的构建提供理论框架。通过尺寸工程形成纳米材料或构筑原子级分散的活性位点,可显著提升催化剂比表面积,提供更高密度的活性位点,还会影响催化剂的内在活性;形貌调控可实现催化剂微结构的精确调控,从增加比表面积、暴露高活性晶面等多种途径影响催化剂活性;缺陷工程能有效调整催化剂的表面成分、电荷分布、电子结构和活性位点,从而影响反应途径、活性和选择性;分子修饰在催化剂表面或内部引入分子,可以促进CO2吸附、稳定中间体、加速电子转移以及抑制活性颗粒的聚集或降解;仿生设计模拟生物体内的环境,通过酶催化\mathrmHCO_3^- 与CO2的快速相互转化,实现CO2的富集,突破低体积分数CO2条件下传质限制的问题,为CO2电催化还原提供了新思路。此外,多设计策略协同可突破单一策略的局限性并充分发挥各策略的优势,进而实现更高的催化性能。在系统梳理催化剂设计策略的同时,介绍了相关策略常用的表征手段和理论计算方法,为策略的有效性提供关键试验验证与机理阐释。然而,当前研究仍面临催化剂在复杂烟气环境下的稳定性差、C2+产物选择性低及工业化应用难等问题,未来通过在模拟烟气或大气条件下对CO2电催化反应机理、催化剂性能等的进一步研究,有望推动低体积分数CO2电催化技术的实际应用,为碳达峰、碳中和目标的实现提供关键科技支撑。

       

      Abstract: The achievement of carbon peak and carbon neutrality goals urgently demands efficient carbon emission reduction and resource utilization technologies. Electrocatalytic CO2 reduction stands out as a key pathway due to numerous advantages, including mild reaction conditions, tunable parameters, and compatibility with renewable energy sources. However, current research predominantly focuses on converting high-purity CO2, while the direct conversion of low-concentration CO2 from major global emission sources (e.g., flue gas from coal-fired power plants containing only ~15% CO2) and the atmospheric environment (~0.04% CO2) faces severe challenges, such as severe mass transfer limitations stemming from low reactant concentration, sluggish reaction kinetics, and low product selectivity. Addressing such bottlenecks necessitates breakthroughs in electrocatalyst design. Building upon an introduction to the mechanism of eCO2RR, this paper specifically analyzes the limiting factors for electrocatalytic low-concentration CO2 reduction. Subsequently, we systematically review design strategies for electrocatalysts targeting low-concentration CO2 conversion, revealing the regulatory logic from microstructure to macroscopic performance. This review aims to provide a theoretical framework for constructing efficient catalytic systems. Size engineering enables the formation of nanomaterials or atomically dispersed active sites, significantly increasing the specific surface area of the catalyst and providing a higher density of active sites, while also influencing intrinsic activity. Morphology control allows precise tuning of catalyst microstructure, enhancing activity through various pathways such as increasing specific surface area and exposing highly active crystal facets. Defect engineering effectively modifies surface composition, charge distribution, electronic structure, and active sites, thereby influencing reaction pathways, activity, and selectivity. Molecular modification, which introduces molecules onto or within the catalyst, can promote CO2 adsorption, stabilize intermediates, accelerate electron transfer, and suppress particle aggregation. Biomimetic Design simulates enzymatic microenvironments to rapidly interconvert \mathrmHCO_3^- and CO2, overcoming mass transfer limitations under low CO2 concentrations. Furthermore, the synergistic integration of multiple design strategies can overcome limitations of individual approaches and maximize their advantages, achieving superior catalytic performance. Alongside the systematic review of catalyst design strategies, relevant characterization techniques and theoretical calculation methods commonly employed are introduced, providing crucial experimental validation and mechanistic insights. Nevertheless, current research still faces challenges such as poor stability of catalysts in complex flue gas environments, low selectivity for C2+ products, and industrial-scale implementation. Future research focusing on the eCO2RR mechanism and catalyst performance under simulated flue gas or atmospheric conditions is expected to promote the practical application of low-concentration CO2 electrocatalytic technology, providing key scientific and technological support for achieving carbon peak and carbon neutrality goals.

       

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