Surface Adsorbed Hydroxyl: A Double-Edged Sword in Electrochemical CO2 Reduction over Oxide-Derived Copper.

Oxide-derived Cu (OD-Cu) featured with surface located sub-20 nm nanoparticles (NPs) created via surface structure reconstruction was developed for electrochemical CO2 reduction (ECO2 RR). With surface adsorbed hydroxyls (OHad ) identified during ECO2 RR, it is realized that OHad , sterically confined and adsorbed at OD-Cu by surface located sub-20 nm NPs, should be determinative to the multi-carbon (C2 ) product selectivity. In situ spectral investigations and theoretical calculations reveal that OHad favors the adsorption of low-frequency *CO with weak C≡O bonds and strengthens the *CO binding at OD-Cu surface, promoting *CO dimerization and then selective C2 production. However, excessive OHad would inhibit selective C2 production by occupying active sites and facilitating competitive H2 evolution. In a flow cell, stable C2 production with high selectivity of ∼60 % at -200 mA cm-2 could be achieved over OD-Cu, with adsorption of OHad well steered in the fast flowing electrolyte.

Decrypting the Controlled Product Selectivity over Ag-Cu Bimetallic Surface Alloys for Electrochemical CO2 Reduction.

Electrochemical CO2 reduction reaction (ECO2 RR) with controlled product selectivity is realized on Ag-Cu bimetallic surface alloys, with high selectivity towards C2 hydrocarbons/alcohols (≈60 % faradaic efficiency, FE), C1 hydrocarbons/alcohols (≈41 % FE) and CO (≈74 % FE) achieved by tuning surface compositions and applied potentials. In situ spectral investigations and theoretical calculations reveal that surface-composition-dependent d-band center could tune *CO binding strengths, regulating the *CO subsequent reaction pathways and then the product selectivity. Further adjusting the applied potentials will alter the energy of participated electrons, which leads to controlled ECO2 RR selectivity towards desired products. A predominant region map, with an indicator proposed to evaluate the thermodynamic predominance of the *CO subsequent reactions, is then provided as a reliable theoretical guidance for the controllable ECO2 RR product selectivity over bimetallic alloys.

Polyacrylate modified Cu electrode for selective electrochemical CO2 reduction towards multicarbon products.

Highly selective production of value-added multicarbon (C2+) products via electrochemical CO2 reduction reaction (eCO2RR) on polycrystalline copper (Cu) remains challenging. Herein, the facile surface modification using poly (α-ethyl cyanoacrylate) (PECA) is presented to greatly enhance the C2+ selectivity for eCO2RR over polycrystalline Cu, with Faradaic efficiency (FE) towards C2+ products increased from 30.1% for the Cu electrode to 72.6% for the obtained Cu-PECA electrode at -1.1 V vs. reversible hydrogen electrode (RHE). Given the well-determined FEs towards C2+ products, the partial current densities for C2+ production could be estimated to be -145.4 mA cm-2 for the Cu-PECA electrode at -0.9 V vs. RHE in a homemade flow cell. In-situ spectral characterizations and theoretical calculations reveal that PECA featured with electron-accepting -C≡N and -COOR groups decorated onto the Cu electrode could inhibit the adsorption of *H intermediates and stabilize the *CO intermediates, given the redistributed interfacial electron density and the raised energy level of d-band center (Ed) of Cu active sites, thus facilitating the C-C coupling and then the C2+ selective production. This study is believed to be guidable to the modification of electrocatalysts and electrodes with polymers to steer the surface adsorption behaviors of reaction intermediates to realize practical eCO2RR towards value-added C2+ products with high activity and selectivity.

Function-switchable metal/semiconductor junction enables efficient photocatalytic overall water splitting with selective water oxidation products.

A novel metal/semiconductor photocatalyst, Cu nanoparticles (NPs) modified TiO2 hollow spheres (Cu/TiO2), was designed for efficient photocatalytic overall water splitting (POWS) under both ultraviolet (UV) and visible (Vis) light. This Cu/TiO2 photocatalyst possesses excellent POWS performance under Vis light at the highest level among the reported TiO2-based photocatalysts. Interestingly, the metal/semiconductor junction formed between Cu and TiO2 enables controlled water-oxidation product selectivity (H2O2 or O2) via different reaction pathways regulated by irradiation wavelengths. Under UV light, the electrons excited in TiO2 are captured by Cu NPs through the Cu/TiO2 Schottky interface for H2 production, with the photoholes in TiO2 producing H2O2 through a two-electron process; whilst under Vis light, Cu NPs act as plasmon to inject hot electrons to TiO2 for H2 production, while O2 is produced by hot holes on Cu NPs via a four-electron process. This rational design of function-switchable metal/semiconductor junction may be helpful to understand the mechanisms for POWS with desired gas/liquid water-oxidation products.

Cascading Interfaces Enable n-Si Photoanodes for Efficient and Stable Solar Water Oxidation.

Interfaces with multifunctions for promoted solid/solid interfacial charge-transfer dynamics and accelerated solid/electrolyte interfacial water redox reaction kinetics are determinative for the photoelectrodes achieving high performances for photoelectrochemical (PEC) water splitting. In this work, well-designed cascading interfaces are introduced in the n-Si photoanode, which is effectively protected by an atomic layer-deposited CoO x thin layer for stabilizing the n-Si photoanode and then coated with an earth-abundant NiCuO x layer for catalyzing the water oxidation reaction. Furthermore, the formed n-Si/CoO x/NiCuO x triple junction could generate a large band bending to provide a considerable photovoltage for promoting the photoinduced charge-transfer and separation processes at the n-Si/CoO x/NiCuO x cascading interfaces. Moreover, at the NiCuO x/electrolyte interface, an in situ electrochemically formed NiCu(OH) x/NiOOH active layer facilitates the water oxidation reaction kinetics. This study demonstrates an alternative approach to stabilize and catalyze n-Si-based photoanodes with cascading interfaces for efficient solar water oxidation.