Designing Copper‐Based Catalysts for Efficient Carbon Dioxide Electroreduction

Abstract

The electroreduction of carbon dioxide (CO2) has been emerging as a high‐ potential approach for CO2 utilization using renewables. When copper (Cu) based catalysts are used, this platform can produce multi‐carbon (C2+) fuels and chemicals with almost net‐zero emission, contributing to the closure of the anthropogenic carbon cycle. Nonetheless, the rational design and development of Cu‐based catalysts are critical toward the realization of highly selective and efficient CO2 electroreduction. In this review, first the latest advances in Cu‐catalyzed CO2 electroreduction in the product selectivity and electrocatalytic activity are briefly summarized. Then, recent theoretical and mechanistic studies of CO2 electroreduction on Cu‐based catalysts are investigated, which serve as programs to design catalysts. Strategies for devising Cu catalysts that aim at promoting different key elementary steps for hydrocarbon and C2+ oxygenates production are further summarized. Moreover, challenges in understanding the mechanism, operando investigation of Cu catalysts and reactions, and systems’ influences are also presented. Finally, the future prospects of CO2 electroreduction are discussed.

Tailoring the Surface and Interface Structures of Copper‐Based Catalysts for Electrochemical Reduction of CO2 to Ethylene and Ethanol

“…[38] The *CO species adsorbed on Cu surface with different configuration, namely, atop-, bridge-, and hollow-bound CO, in which the CO species coordinate with one, two, and more than three Cu atoms, respectively. [3,39,40] The adsorption states of *CO strongly determine the binding energy of *CO on Cu surface, which is crucial for further hydrogenation process and regulates product distribution. [15,21] This also explains the capability of Cu for catalyzing CO 2 electroreduction to hydrocarbons and multi-carbon products.…”

“…formed from CO 2 RR, ethylene and ethanol are highly desired because the widely industrial applications with the huge market demand. [3,4] It is reported that the global ethylene market is expected to grow from $190.29 billion in 2020 to $302.22 billion in 2025 with a compound annual growth rate (CAGR) of 7%, [5] and the ethanol market estimated at $87.4 billion in 2020, is projected to reach $137.4 billion with a CAGR of 6.7%. [6] Therefore, electrochemical reduction of the greenhouse gas CO 2 to produce ethylene and ethanol not only lowers the CO 2 emission, improves the atmospheric environment, and stores the renewable energy, but also has great economic benefits (Figure 1).…”

“…Although several review and perspective papers about Cubased catalysts or all the catalysts for CO 2 RR have been published, most of them focus on the comprehensive progress of catalysts for the all products and the characteristics of catalysts for each product are not clear enough. [2,3,8,10,12,[35][36][37] In this review, we only focus on the two very important products of ethylene and ethanol, and systematically discuss the surface and interface structure effects of Cu-based catalysts for CO 2 -to-ethylene and CO 2 -to-ethanol conversions. The influence factors of activity and selectivity are summarized in detail and the structure-performance relationship of the catalyst for ethylene or ethanol is clearly displayed, especially combined with the recent important progresses.…”

Recent development of nanomaterials for carbon dioxide electroreduction

“…For example, Co‐SAC coordinated with four nitrogen is an effective catalyst for HER, 44 but its molecular analogs such as cobalt porphyrin (CoP) and cobalt phthalocyanine (CoPc) are highly active in CO 2 ‐to‐CO electroreduction 45,46 . Table 1 shows the performance of some examples of SACs for CO 2 RR, such as Fe‐, 47–49,65–71 Co‐, 52,53,72,73 Ni‐, 74–87 Cu‐, 20,62,88–90 Zn‐, 58,59,91 and Sn‐based 60,61 ones 50,51,54–57,63,64 . Most of these SACs produced CO.…”

Local Environment Determined Reactant Adsorption Configuration for Enhanced Electrocatalytic Acetone Hydrogenation to Propane

“…[4,24,25,28,33] So far, almost all attempts in tuning adsorption configuration of above-mentioned carbon/oxygen-containing intermediates were carried out through catalyst engineering,i .e., designing materials with as pecific electronic structure,which can lead to the desired adsorption ability toward the reactants and intermediates,thus determining the reaction pathway to target products. [6,34,35] However, such strategy has clear limitations:o no ne hand, it is effortconsuming to fabricate acatalyst with the exact desired active sites and electronic structures.O nt he other,m ethods for tuning intermediate status on designed catalysts are exceptional cases that can hardly be used as universal guidance on other catalysts.Itiscrucial to develop amore general strategy to control the adsorption configuration of intermediates by universal means.InCRR, many attempts have been made to control the product selectivity by adjusting the local reaction environment of the catalyst surface. [36][37][38][39] By applying af low cell reactor with ag as-diffusion-electrode (GDE), it was found that the concentration of local OH À ion has asignificant influence on the adsorption configuration of some complex intermediates (e.g., * CO-COH, * OCH 2 CH 3 )and C2 products selectivity.…”