近日，上海交通大学贺玉莲团队研究了NiFe/TiO₂双金属催化CO₂加氢的常压C-C偶联。相关论文于2025年9月4日发表在《美国化学会志》上。

二氧化碳催化升级为增值C₂₊产品提供了有前景的解决方案，以减少碳排放并获得额外的经济效益。

研究组报道了一种NiFe双金属催化剂，在H₂预处理温度下具有高效的常压C-C耦合性能。在350℃下还原NiFe/TiO₂ （NiFe-350/TiO₂）达到最佳性能，在350℃常压下CO₂转化率为27.8%，对C₂-C₃烃（主要是乙烷）的选择性为33.9%。采用原位表征、动力学、中间控制实验和第一线原理计算的组合研究表明，NiFe-350/TiO₂中形成了部分氧化的Ni^δ+ -O-Fe^δ+，其双位点协同作用增强了CO₂活化，并促进了H₂异裂解活化成H^δ-物种，这些物种选择性地将*CO₂氢化为HCOO*和*CH₃O中间体，从而抑制CO副产物的形成，并可能通过不对称的*CH₂-CH₃偶联机制产生有效的大气压C-C偶联。

与之形成鲜明对比的是，完全还原的NiFe双金属催化剂更倾向于直接的CO₂解离途径，而不是形成易于从表面解吸的*CO，以及均溶H₂活化，从而不利于C-C偶联过程。简而言之，该工作报道了二氧化碳直接加氢常压合成C₂-C₃石蜡，为有效的碳链传播提供了设计依据。

附：英文原文

Title: Ambient-Pressure C–C Coupling of CO2 Hydrogenation by NiFe/TiO2 Bimetallic Catalyst

Author: Mingxin Jiang, Zhi-Qiang Wang, Zhuo Li, Zhisong Liu, Yiwei Yin, Feixiang Tian, Anyu Li, Haomiao Xu, Xue-Qing Gong, Yulian He

Issue&Volume: September 4, 2025

Abstract: Catalytic upgrading of CO2 to value-added C2+ products offers promising solutions to trim carbon emissions with additional economic benefits. Herein, we report a NiFe bimetallic catalyst showing efficient ambient-pressure C–C coupling performance subject to H2 pretreatment temperature. An optimal performance was achieved after reducing NiFe/TiO2 at 350 °C (NiFe-350/TiO2), yielding 27.8% CO2 conversion and 33.9% selectivity to C2–C3 hydrocarbon (primarily ethane) at 350 °C under atmospheric pressure. Combinatorial studies employing in situ characterizations, kinetic, intermediate control experiments and first-principles calculations indicate the formation of partially oxidized Niδ+–O–Feδ+ in NiFe-350/TiO2, the dual-site synergy of which enhances CO2 activation and facilitates H2 heterolytic activation into Hδ species that selectively hydrogenate *CO2 into HCOO* and *CH3O intermediates, thus suppressing CO byproduct formation and resulting in effective ambient-pressure C–C coupling likely via an asymmetric *CH2–CH3 coupling mechanism. In stark contrast, the fully reduced NiFe bimetallic catalyst favors a direct CO2 dissociation pathway instead to form *CO that easily desorbs from the surface, as well as homolytic H2 activation such that the C–C coupling process is unfavored. In brief, this work reports the ambient-pressure synthesis of C2–C3 paraffins from direct CO2 hydrogenation and provides design rationales for efficient carbon chain propagation.

DOI: 10.1021/jacs.5c07878

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c07878