The limited selectivity of existing CO2 reduction catalysts and rising levels of CO2 in the atmosphere necessitate the identification of specific structure–reactivity relationships to inform catalyst development. Herein, we develop a predictive framework to tune the selectivity of CO2 reduction on Cu by examining a series of polymeric and molecular modifiers. We find that protic species enhance selectivity for H2, hydrophilic species enhance formic acid formation, and cationic hydrophobic species enhance CO selectivity. ReaxFF reactive molecular dynamics simulations indicate that the hydrophilic/hydrophobic modifiers influence the formation of surface hydrides, which yield formic acid or H2. These observations offer insights into how these modifiers influence catalytic behavior at the non-precious Cu surface and may aid in the future implementation of organic structures in CO2 reduction devices.

Dinickel bisphenoxyiminato complexes based on highly substituted p- and m-terphenyl backbones were synthesized, and the corresponding atropisomers were isolated. In the presence of a phosphine scavenger, Ni(COD)2, the phosphine-ligated syn-dinickel complexes copolymerized α-olefins and ethylene in the presence of amines to afford 0.2–1.3% α-olefin incorporation and copolymerized amino olefins and ethylene with a similar range of incorporation (0.1–0.8%). The present rigid catalysts provide a bimetallic strategy for insertion polymerization of polar monomers without masking of the heteroatom group. The effects of the catalyst structure on the reactivity were studied by comparisons of the syn and anti atropisomers and the p- and m-terphenyl systems.

Electrochemical CO2 reduction is an attractive option for storing renewable electricity and for the sustainable production of valuable chemicals and fuels. In this roadmap, we review recent progress in fundamental understanding, catalyst development, and in engineering and scale-up. We discuss the outstanding challenges towards commercialization of electrochemical CO2 reduction technology: energy efficiencies, selectivities, low current densities, and stability. We highlight the opportunities in establishing rigorous standards for benchmarking performance, advances in in operando characterization, the discovery of new materials towards high value products, the investigation of phenomena across multiple-length scales and the application of data science towards doing so. We hope that this collective perspective sparks new research activities that ultimately bring us a step closer towards establishing a low- or zero-emission carbon cycle.

Using P nuclear magnetic resonance (NMR) spectroscopy, we monitor the competition between tri- n-butylphosphine (BuP) and various amine and phosphine ligands for the surface of chloride terminated CdSe nanocrystals. Distinct P NMR signals for free and bound phosphine ligands allow the surface ligand coverage to be measured in phosphine solution. Ligands with a small steric profile achieve higher surface coverages (BuP = 0.5 nm, MeP- n-octyl = 2.0 nm, NHBu = >3 nm) and have greater relative binding affinity for the nanocrystal (binding affinity: MeP > MeP- n-octyl ∼ MeP- n-octadecyl > EtP > BuP). Among phosphines, only BuP and MeP- n-octyl support a colloidal dispersion, allowing a relative surface binding affinity ( K) to be estimated in that case ( K = 3.1). The affinity of the amine ligands is measured by the extent to which they displace BuP from the nanocrystals ( K: HNBu ∼ N- n-butylimidazole > 4-ethylpyridine > BuP ∼ HNBu > MeNBu > BuN). The affinity for the CdSe surface is greatest among soft, basic donors and depends on the number of each ligand that bind. Sterically unencumbered ligands such as imidazole, pyridine, and n-alkylamines can therefore outcompete stronger donors such as alkylphosphines. The influence of repulsive interactions between ligands on the binding affinity is a consequence of the high atom density of binary semiconductor surfaces. The observed behavior is distinct from the self-assembly of straight-chain surfactants on gold and silver where the ligands are commensurate with the underlying lattice and attractive interactions between aliphatic chains strengthen the binding.

We elucidate the role of subsurface oxygen on the production of C2 products from CO2 reduction over Cu electrocatalysts using the newly developed grand canonical potential kinetics density functional theory method, which predicts that the rate of C2 production on pure Cu with no O is ∼500 times slower than H2 evolution. In contrast, starting with Cu2O, the rate of C2 production is >5,000 times faster than pure Cu(111) and comparable to H2 production. To validate these predictions experimentally, we combined time-dependent product detection with multiple characterization techniques to show that ethylene production decreases substantially with time and that a sufficiently prolonged reaction time (up to 20 h) leads only to H2 evolution with ethylene production ∼1,000 times slower, in agreement with theory. This result shows that maintaining substantial subsurface oxygen is essential for long-term C2 production with Cu catalysts.