Jingxuan Song, Yuexian Du, Lu Liu, Kunfan Dong, Ziyu Deng, Yanghe Fu, Yijing Gao, Fumin Zhang, Fa Yang, Weidong Zhu and Maohong Fan
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引用次数: 0
摘要
电化学CO2还原为将CO2转化为增值化学品和燃料提供了一条可持续的途径,解决了与温室气体排放相关的能源可持续性和环境修复的关键挑战。然而,开发高效耐用的选择性甲酸(HCOOH)电催化剂仍然是一个关键的挑战。在此,我们报告了一种具有成本效益的氮掺杂碳负载铋纳米颗粒(Bi@NC)催化剂,该催化剂来源于铋基金属有机框架(MOF)的可控热解,并可调节双氰胺的掺入。优化后的Bi@NC在传统的h电池配置下,在−1.1 V下以96%的法拉第效率实现了出色的co2到hcooh的转换。此外,在流动电池中连续电解12小时期间,Bi@NC在- 1.7 V下保持稳定的- 220 mA cm - 2电流密度,同时保持HCOOH的法拉第效率超过90%,突出了其在苛刻条件下的稳稳性。结合实验和计算分析表明,在碳基体中引入杂原子N不仅可以促进Bi纳米粒子的分散,通过Bi - N - c界面的电荷重分配增强CO2的吸附/活化,还可以通过电子结构调制选择性地稳定*COOH中间体,促进电化学CO2还原过程中甲酸盐的生成。本研究建立了mof衍生电催化剂的合理设计策略,为高效的co2 - hcooh转化体系的杂原子工程提供了新的见解。
MOF-derived Bi@NC electrocatalysts with heteroatomic engineering for high-efficiency CO2-to-formate conversion†
Electrochemical CO2 reduction offers a sustainable pathway to convert CO2 into value-added chemicals and fuels, addressing critical challenges of energy sustainability and environmental remediation associated with greenhouse gas emissions. However, developing efficient and durable electrocatalysts for selective formic acid (HCOOH) generation remains a critical challenge. Herein, we report a cost-effective nitrogen-doped carbon-supported bismuth nanoparticle (Bi@NC) catalyst derived from controlled pyrolysis of a bismuth-based metal–organic framework (MOF) with tunable dicyandiamide incorporation. The optimized Bi@NC achieves exceptional CO2-to-HCOOH conversion with 96% faradaic efficiency at −1.1 V in a conventional H-cell configuration. Furthermore, during a 12-hour continuous electrolysis in a flow cell, Bi@NC maintains a stable current density of −220 mA cm−2 at −1.7 V vs. RHE while retaining a faradaic efficiency for HCOOH of above 90%, highlighting its robustness under demanding conditions. Combined experimental and computational analyses reveal that the introduction of heteroatomic N into the carbon matrix can not only facilitate the dispersion of Bi nanoparticles and enhance the adsorption/activation of CO2 through charge redistribution at the Bi–N–C interfaces, but also selectively stabilize *COOH intermediates via electronic structure modulation, promoting formate generation in electrochemical CO2 reduction. This work establishes a rational design strategy for MOF-derived electrocatalysts, offering new insights into heteroatomic engineering for efficient CO2-to-HCOOH conversion systems.
期刊介绍:
Green Chemistry is a journal that provides a unique forum for the publication of innovative research on the development of alternative green and sustainable technologies. The scope of Green Chemistry is based on the definition proposed by Anastas and Warner (Green Chemistry: Theory and Practice, P T Anastas and J C Warner, Oxford University Press, Oxford, 1998), which defines green chemistry as the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. Green Chemistry aims to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. The journal welcomes submissions on all aspects of research relating to this endeavor and publishes original and significant cutting-edge research that is likely to be of wide general appeal. For a work to be published, it must present a significant advance in green chemistry, including a comparison with existing methods and a demonstration of advantages over those methods.