Cu-Based Materials for Enhanced C2+ Product Selectivity in Photo-/Electro-Catalytic CO2 Reduction: Challenges and Prospects

Abstract

Carbon dioxide conversion into valuable products using photocatalysis and electrocatalysis is an effective approach to mitigate global environmental issues and the energy shortages. Among the materials utilized for catalytic reduction of CO2, Cu-based materials are highly advantageous owing to their widespread availability, cost-effectiveness, and environmental sustainability. Furthermore, Cu-based materials demonstrate interesting abilities in the adsorption and activation of carbon dioxide, allowing the formation of C2+ compounds through C–C coupling process. Herein, the basic principles of photocatalytic CO2 reduction reactions (PCO2RR) and electrocatalytic CO2 reduction reaction (ECO2RR) and the pathways for the generation C2+ products are introduced. This review categorizes Cu-based materials into different groups including Cu metal, Cu oxides, Cu alloys, and Cu SACs, Cu heterojunctions based on their catalytic applications. The relationship between the Cu surfaces and their efficiency in both PCO2RR and ECO2RR is emphasized. Through a review of recent studies on PCO2RR and ECO2RR using Cu-based catalysts, the focus is on understanding the underlying reasons for the enhanced selectivity toward C2+ products. Finally, the opportunities and challenges associated with Cu-based materials in the CO2 catalytic reduction applications are presented, along with research directions that can guide for the design of highly active and selective Cu-based materials for CO2 reduction processes in the future.

Perovskite Paradigm Shift: A Green Revolution with Lead-Free Alternatives in Photocatalytic CO2 Reduction

“…The transformation of CO 2 to C 2 products and oxygenated chemicals, including but not limited to ethylene (C 2 H 4 ), ethane (C 2 H 6 ), methanol (CH 3 OH), formic acid (HCOOH), and ethanol (C 2 H 5 OH), can be of greater interest than CO and CH 4 due to their significant industrial use. 346,347 However, the generation of these higher added value products holds a formidable challenge due to the complex reaction pathway and competing reactions. One of the key strategies for obtaining C 2 products lies in the effective stabilization of C 1 radicals or intermediates and their engagement in C−C coupling reactions.…”

“…Based on the available literature as summarized in Table , the product selectivity is underexplored, in which almost all LFHPs have been reported for C 1 products, i.e., CO and CH 4 . The transformation of CO 2 to C 2 products and oxygenated chemicals, including but not limited to ethylene (C 2 H 4 ), ethane (C 2 H 6 ), methanol (CH 3 OH), formic acid (HCOOH), and ethanol (C 2 H 5 OH), can be of greater interest than CO and CH 4 due to their significant industrial use. , However, the generation of these higher added value products holds a formidable challenge due to the complex reaction pathway and competing reactions. One of the key strategies for obtaining C 2 products lies in the effective stabilization of C 1 radicals or intermediates and their engagement in C–C coupling reactions. , To selectively improve C–C coupling catalysis reaction over LFHP-based materials, the electron-rich graphene can be composited.…”

Nanomaterial-based energy conversion and energy storage devices: a comprehensive review

“…Efficient CO 2 conversion using electro-catalytic CO 2 reduction involves protonation and intermediate COOH generation. 228 Finding effective catalytic materials is crucial for increased catalytic activity. In this case, the Mo-edge sites of MoS 2 nanosheets can synthesize critical intermediate *COOH with a lower Gibbs free energy due to their metallic characteristics and high d-electron density.…”

Synergistic effect of atomically dispersed Cu species and Ti-defects for boosting photocatalytic CO2 reduction over hierarchical TiO2

“…This, along with their unique adsorption properties for reactants and intermediates during CO 2 reduction reactions, enables the modulation of reaction paths. 33,34 However, conventional post-treatment strategies such as impregnation methods often face challenges like low single-atom loading, irreversible aggregation due to the high surface energy of single atoms, and difficulties in elucidating the chemical environment of atoms and their catalytic mechanisms during in situ reactions. 35 To overcome these limitations, doping copper species into the TiO 2 lattice by occupying Ti atomic sites while ensuring effective surface exposure could lead to single-atom dispersion of Cu species.…”