Electrochemical and photochemical carbon dioxide reduction reactions (CO2RR) represent pivotal strategies for converting CO2 into valuable chemicals, yet their multistep pathways and transient intermediates complicate the identification of the rate‐determining step (RDS). Kinetic isotope effects (KIEs) provide bond‐sensitive evidence by revealing how isotopic substitution changes reaction rates. This Perspective critically examines the application of KIEs to investigate CO2 activation, C─H bond formation, C─C coupling, water activation, and interfacial hydrogen transfer. Across these processes, normal, inverse, and near‐unity KIEs, when combined with spectroscopy and theoretical calculations, help distinguish competing elementary steps and reaction pathways. Isotope‐dependent product abundances further differentiate Langmuir–Hinshelwood and Eley–Rideal hydrogen transfer pathways and reveal how catalyst structure and interfacial environments regulate reaction pathways and selectivity. Finally, we discuss advances in isotope‐resolved operando detection, broader application of isotope analysis, and closer integration with theoretical calculations as opportunities to strengthen mechanistic analysis of CO2RR.
Catalytic CO2 reduction reaction (CO2RR) offers a promising approach for converting CO2 into value-added chemicals and fuels. However, its practical development remains limited by unfavorable reaction energetics, competition from the hydrogen evolution reaction (HER), and complex product selectivity. Conventional catal...
Dong-Qiu Zhao, Shan Xu, Bie Mei et al.· Inorganics· 0 citations
While electrolyte cations are widely recognized as a key regulator of electrochemical CO2 reduction (CO2RR) activity, whether different cation classes merely modulate reaction rates or fundamentally redirect the underlying rate-determining step (RDS), and consequently the system's response to environmental variables,...
Sejin Park, Gwangsu Bak, Jiseon Kim et al.· ACS Catalysis· 0 citations
Pathways and selectivities for oxygen reduction (ORR) on nanoparticle catalysts respond sensitively to the addition of exogenous redox mediators, and recent findings indicate organic surface redox mediators influence formation rates for hydrogen peroxide (H2O2) and water. Here, the introduction of carbon dioxide (CO2)...
Sucharita Vijayaraghavan, Hung-Ling Yu, Adam J. Senko et al.· Chemical Science· 0 citations
Electrochemical two-electron CO2 reduction (2e– CO2RR) to carbon monoxide (CO) and formic acid (HCOOH) on single-atom catalysts (SACs) has long been rationalized by independent reaction pathways initiated from distinct CO2 adsorption modes. Here, employing constant-potential ab initio molecular dynamics (AIMD) simula...
H. Jung, Wooseok Lee, Juyeon Lee et al.· Journal of Physical Chemistr...· 0 citations
Solid-state hydrides combine hydrogen storage with the direct reduction of CO2, which opens an alternative route for carbon capture and utilisation. This review examines the use of ionic, complex and transition-metal-based ternary hydrides as reactive media for the conversion of gaseous CO2 and solid inorganic carbonat...
G. Amica, M. L. Grasso, Julian Puszkiel Saldivar et al.· Chemical Communications· 0 citations
The ever-escalating accumulation of atmospheric CO2 and the growing demand for renewable energy conversion and storage have intensified research into solar-driven CO2 utilization technologies. Photothermal catalytic CO2 hydrogenation to methane has emerged as a promising approach for simultaneous carbon resource recy...
Shi-Kang Xiao, Li-Ge Wang, Yi-Ting Huo et al.· ACS Catalysis· 0 citations
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