Electrocatalytic CO₂ Reduction over Atomically Precise Metal Nanoclusters Protected by Organic Ligands

Abstract

The electrochemical carbon dioxide reduction reaction (CO2RR) is a promising method to realize carbon recycling and sustainable development because of its mild reaction conditions and capability to utilize the electric power generated by renewable energy such as solar, wind, or tidal energy to produce high-value-added liquid fuels and chemicals. However, it is still a great challenge to deeply understand the reaction mechanism of CO2RRs involving multiple chemical processes and multiple products due to the complexity of the traditional catalyst’s surface. Organic ligand-protected metal nanoclusters (NCs) with accurate compositions and definite atom packing structures show advantages for revealing the reaction mechanism of CO2RRs. This Review focuses on the recent progress in CO2RRs catalyzed by atomically precise metal NCs, including gold, copper, and silver NCs. Particularly, the influences of charge, ligand, surface structure, doping of Au NCs, and binders on the CO2RR are discussed in detail. Meanwhile the reaction mechanisms of CO2RRs including the active sites and the key reaction intermediates are also discussed. It is expected that progress in this research area could promote the development of metal NCs and CO2RRs.

Size Effects of Atomically Precise Gold Nanoclusters in Catalysis

“…Compared to the bare clusters, the ligand-protected NCs exhibit more complex catalytic behavior . Recent years have witnessed extensive research in exploring ligand-protected NCs, including new catalytic reactions for NCs, − the morphology effect, , the intriguing ligand effects, − theoretical simulations, , etc., albeit these are still less systematic studies on the size effects.…”

All-alkynyl-protected coinage metal nanoclusters: from synthesis to electrocatalytic CO2reduction applications

“…86 Recent high-quality review papers regarding metal nanoclusters for eCO 2 RR mainly focus on the thiolate ligand, whereas a systematic summary of alkynyl-protected metal clusters for eCO 2 RR is missing. 67,87,88 Here, we mainly discuss allalkynyl-protected Au and Ag nanoclusters for eCO 2 RR, with particular attention on elucidating the metal core effect and the surface ligand effect.…”

Cascade Catalysis for the Hydrogenation of Carbon Dioxide to Methyl Formate Using a Molecular Ru–Phosphine Complex and the Metal–Organic Framework UiO-66 as Heterogeneous Acid

“…Carbon capture, storage, and utilization (CCSU) is therefore considered as extremely important, and major steps forward are being made toward carbon-neutral energy systems. , However, the utilization of this C 1 building block as feedstock typically requires purification from diluted sources by solvent absorption (e.g., amines, KOH solution, ...) and energy intensive desorption . More recently, approaches were made to completely eliminate this desorption step, converting CO 2 directly into useful products such as formic acid/formate, − methanol, , oxazolidones, , urea, syngas, carbonates and methyl formate. , …”