Less-Coordinated Atomic Copper-Dimer Boosted Carbon-Carbon Coupling During Electrochemical CO2 Reduction.

This work reports a metal-organic framework (MOF) with less-coordinated copper dimers, which displays excellent electrochemical CO2 reduction (eCO2 RR) performance with an advantageous current density of 0.9 A cm-2 and a high Faradaic efficiency of 71% to C2 products. In comparison with MOF with Cu monomers that are present as Cu1 O4 with a coordination number of 3.8 ± 0.2, Cu dimers exist as O3 Cu1 ···Cu2 O2 with a coordination number of 2.8 ± 0.1. In situ characterizations together with theoretical calculations reveal that two *CO intermediates are stably adsorbed on each site of less-coordinated Cu dimers, which favors later dimerization via a key intermediate of *CH2 CHO. The highly unsaturated dual-atomic Cu provides large-quantity and high-quality actives sites for carbon-carbon coupling, achieving the optimal trade-off between activity and selectivity of eCO2 RR to C2 products.

Efficient solar fuel production with a high-pressure CO2-captured liquid feed.

We demonstrated an efficient solar photovoltaic-powered electrochemical CO2 reduction device with a high-pressure CO2-captured liquid feed. In an "air-to-barrel" picture, this device holds promise to avoid both high-temperature gaseous CO2 regeneration and high energy-cost gas product separation steps, while these steps are necessary for devices with a gaseous CO2 feed. To date, solar fuel production with a CO2-saturated liquid feed suffers from high over-potential to suppress the hydrogen evolution reaction and consequently, low solar-to-chemical (STC) energy conversion efficiency. Here, we presented a distinct high-pressure operando strategy, i.e., we took extra advantage of the high pressure in catalyst synthesis besides in the period of the CO2 reduction reaction (CO2RR). The power of this strategy was demonstrated by a proof-of-concept device in which a representative copper catalyst was first synthesized in operando in a high-pressure (50 bar) CO2-saturated KHCO3 solution, and then this high-pressure CO2-captured liquid was converted to solar fuel using the operando synthesized Cu catalyst. This Cu catalyst achieved 95% CO2RR selectivity at the recorded low potential of -0.3 V vs. RHE enabled by the combination of operando facet engineering and oxide derivation. Furthermore, this device achieved a record-high STC efficiency of 21.6% under outdoor illumination, superior to other CO2-saturated liquid-fed devices, and compared favorably to gaseous CO2-fed devices.

Electrochemical Reduction of CO2 to HCOOH over Copper Catalysts.

Although great progress has been made in the field of electrochemical CO2 reduction reaction (eCO2RR), inducing product selectivity is still difficult. We herein report that a thiocyanate ion (SCN-) switched the product selectivity of copper catalysts for eCO2RR in an H-cell. A cuprous thiocyanate-derived Cu catalyst was found to exhibit excellent HCOOH selectivity (faradaic efficiency = 70-88%) over a wide potential range (-0.66 to -0.95 V vs RHE). Furthermore, it was revealed that the formation of CO and C2H4 over commercial copper electrodes could be dramatically suppressed with the presence of SCN-, switching to HCOOH. Density functional theory calculations disclosed that SCN- made the formation of HCOO* easier than COOH* on Cu (211), facilitating the HCOOH generation. Our results provide a new insight into eCO2RR and will be helpful in the development of cheap electrocatalysts for specific utilization.