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Improving the kinetics and selectivity of CO2/CO electroreduction to valuable multi-carbon products is a challenge for science and is a requirement for practical relevance. Here we develop a thiol-modified surface ligand strategy that promotes electrochemical CO-to-acetate. We explore a picture wherein nucleophilic interaction between the lone pairs of sulfur and the empty orbitals of reaction intermediates contributes to making the acetate pathway more energetically accessible. Density functional theory calculations and Raman spectroscopy suggest a mechanism where the nucleophilic interaction increases the sp2 hybridization of CO(ad), facilitating the rate-determining step, CO* to (CHO)*. We find that the ligands stabilize the (HOOC-CH2)* intermediate, a key intermediate in the acetate pathway. In-situ Raman spectroscopy shows shifts in C-O, Cu-C, and C-S vibrational frequencies that agree with a picture of surface ligand-intermediate interactions. A Faradaic efficiency of 70% is obtained on optimized thiol-capped Cu catalysts, with onset potentials 100 mV lower than in the case of reference Cu catalysts.

Alkali hydroxide systems capture CO2 as carbonate; however, generating a pure CO2 stream requires significant energy input, typically from thermal cycling to 900°C. What is more, the subsequent valorization of gas-phase CO2 into products presents additional energy requirements and system complexities, including managing the formation of (bi)carbonate in an electrolyte and separating unreacted CO2 downstream. Here, we report the direct electrochemical conversion of CO2, captured in the form of carbonate, into multicarbon (C2+) products. Using an interposer and a Cu/CoPc-CNTs electrocatalyst, we achieve 47% C2+ Faradaic efficiency at 300 mA cm−2 and a full cell voltage of 4.1 V. We report 56 wt % of C2H4 and no detectable C1 gas in the product gas stream: CO, CH4, and CO2 combined total below 0.9 wt % (0.1 vol %). This approach obviates the need for energy to regenerate lost CO2, an issue seen in prior CO2-to-C2+ reports.

Two-electron oxygen reduction offers a route to H2O2 that is potentially cost-effective and less energy-intensive than the industrial anthraquinone process. However, the catalytic performance of the highest performing prior heterogeneous electrocatalysts to H2O2 has lain well below the >300 mA cm−2 needed for capital efficiency. Herein, guided by computation, we present a supramolecular approach that utilizes oxygen functional groups in a carbon nanotube substrate that—when coupled with a cobalt phthalocyanine catalyst—improve cobalt phthalocyanine adsorption, preventing agglomeration; and that further generate an electron-deficient Co centre whose interaction with the key H2O2 intermediate is tuned towards optimality. The catalysts exhibit an overpotential of 280 mV at 300 mA cm−2 with turnover frequencies over 50 s−1 in a neutral medium, an order of magnitude higher activity compared with the highest performing prior H2O2 electrocatalysts. This performance is sustained for over 100 h of operation. [Figure not available: see fulltext.].

Performing CO2 reduction in acidic conditions enables high single-pass CO2 conversion efficiency. However, a faster kinetics of the hydrogen evolution reaction compared to CO2 reduction limits the selectivity toward multicarbon products. Prior studies have shown that adsorbed hydroxide on the Cu surface promotes CO2 reduction in neutral and alkaline conditions. We posited that limited adsorbed hydroxide species in acidic CO2 reduction could contribute to a low selectivity to multicarbon products. Here we report an electrodeposited Cu catalyst that suppresses hydrogen formation and promotes selective CO2 reduction in acidic conditions. Using in situ time-resolved Raman spectroscopy, we show that a high concentration of CO and OH on the catalyst surface promotes C-C coupling, a finding that we correlate with evidence of increased CO residence time. The optimized electrodeposited Cu catalyst achieves a 60% faradaic efficiency for ethylene and 90% for multicarbon products. When deployed in a slim flow cell, the catalyst attains a 20% energy efficiency to ethylene, and 30% to multicarbon products.

Microfluidics experiments were used to examine mineral dissolution-precipitation reactions under evaporative conditions and identify pore-scale processes that control reaction rate. The entrainment of reacting mineral particles by a mobile water-gas interface driven by evaporation dramatically altered the relative abundance of reactive mineral surface area to fluid reservoir volume. This ratio, which directly influences reaction rate and reaction progress, was observed to vary by nearly two orders of magnitude as evaporation progressed in the experiments. Its dynamic evolution may have a correspondingly large impact on mineral-fluid reaction in Earth's shallow subsurface. We predict that the spatial and temporal variability of pore-scale reaction rates will be significant during evaporation, imbibition, or drainage in the vadose zone, with implications for chemical weathering, soil quality, and carbon cycling. Variable reaction rates during particle mobility are likely to be of increased significance as global rainfall patterns and soil moisture contents evolve in response to climate change.