Modulation of *CHxO Adsorption to Facilitate Electrocatalytic Reduction of CO2 to CH4 over Cu-Based Catalysts.

Copper (Cu) can efficiently catalyze the electrochemical CO2 reduction reaction (CO2RR) to produce value-added fuels and chemicals, among which methane (CH4) has drawn attention due to its high mass energy density. However, the linear scaling relationship between the adsorption energies of *CO and *CHxO on Cu restricts the selectivity toward CH4. Alloying a secondary metal in Cu provides a new freedom to break the linear scaling relationship, thus regulating the product distribution. This paper describes a controllable electrodeposition approach to alloying Cu with oxophilic metal (M) to steer the reaction pathway toward CH4. The optimized La5Cu95 electrocatalyst exhibits a CH4 Faradaic efficiency of 64.5%, with the partial current density of 193.5 mA cm-2. The introduction of oxophilic La could lower the energy barrier for *CO hydrogenation to *CHxO by strengthening the M-O bond, which would also promote the breakage of the C-O bond in *CH3O for the formation of CH4. This work provides a new avenue for the design of Cu-based electrocatalysts to achieve high selectivity in CO2RR through the modulation of the adsorption behaviors of key intermediates.

Back-illuminated photoelectrochemical flow cell for efficient CO2 reduction.

Photoelectrochemical CO2 reduction reaction flow cells are promising devices to meet the requirements to produce solar fuels at the industrial scale. Photoelectrodes with wide bandgaps do not allow for efficient CO2 reduction at high current densities, while the integration of opaque photoelectrodes with narrow bandgaps in flow cell configurations still remains a challenge. This paper describes the design and fabrication of a back-illuminated Si photoanode promoted PEC flow cell for CO2 reduction reaction. The illumination area and catalytic sites of the Si photoelectrode are decoupled, owing to the effective passivation of defect states that allows for the long minority carrier diffusion length, that surpasses the thickness of the Si substrate. Hence, a solar-to-fuel conversion efficiency of CO of 2.42% and a Faradaic efficiency of 90% using Ag catalysts are achieved. For CO2 to C2+ products, the Faradaic efficiency of 53% and solar-to-fuel of 0.29% are achieved using Cu catalyst in flow cell.

SrO-layer insertion in Ruddlesden-Popper Sn-based perovskite enables efficient CO2 electroreduction towards formate.

Tin (Sn)-based oxides have been proved to be promising catalysts for the electrochemical CO2 reduction reaction (CO2RR) to formate (HCOO-). However, their performance is limited by their reductive transformation into metallic derivatives during the cathodic reaction. This paper describes the catalytic chemistry of a Sr2SnO4 electrocatalyst with a Ruddlesden-Popper (RP) perovskite structure for the CO2RR. The Sr2SnO4 electrocatalyst exhibits a faradaic efficiency of 83.7% for HCOO- at -1.08 V vs. the reversible hydrogen electrode with stability for over 24 h. The insertion of the SrO-layer in the RP structure of Sr2SnO4 leads to a change in the filling status of the anti-bonding orbitals of the Sn active sites, which optimizes the binding energy of *OCHO and results in high selectivity for HCOO-. At the same time, the interlayer interaction between interfacial octahedral layers and the SrO-layers makes the crystalline structure stable during the CO2RR. This study would provide fundamental guidelines for the exploration of perovskite-based electrocatalysts to achieve consistently high selectivity in the CO2RR.

The effect of specific adsorption of halide ions on electrochemical CO2 reduction.

In the electrochemical CO2 reduction reaction (CO2RR), halide ions could impose a significant effect on multi-carbon (C2+) product production for Cu-based catalysts by a combined contribution from various mechanisms. However, the nature of specific adsorption of halide ions remains elusive due to the difficulty in decoupling different effects. This paper describes a facile method to actively immobilize the morphology of Cu-based catalysts during the CO2RR, which makes it possible to reveal the fundamental mechanism of specific adsorption of halide ions. A stable morphology is obtained by pre-reduction in aqueous KX (X = Cl, Br, I) electrolytes followed by conducting the CO2RR using non-buffered and non-specifically adsorbed K2SO4 as the supporting electrolyte, by which the change of local pH and cation concentration is also maintained during the CO2RR. In situ spectroscopy revealed that the specific adsorption of halide ions enhances the adsorption of *CO intermediates, which enables a high selectivity of 84.5% for C2+ products in 1.0 M KI.