Toward High-Performance CO2 -to-C2 Electroreduction via Linker Tuning on MOF-Derived Catalysts.

Copper (Cu)-based metal-organic frameworks (MOFs) and MOF-derived catalysts are well studied for electroreduction of carbon dioxide (CO2 ); however, the effects of organic linkers for the selectivity of CO2 reduction are still unrevealed. Here, a series of Cu-based MOF-derived catalysts is investigated with different organic linkers appended, named X-Cu-BDC (BDC = 1,4-benzenedicarboxylic acid, X = NH2 , OH, H, F, and 2F). It is found that the linkers affect the faradaic efficiency (FE) for C2 products with an order of NH2  < OH < bare Cu-BDC < F < 2F, thus tuning the FEC2 :FEC1 ratios from 0.6 to 3.8. As a result, the highest C2 FE of ≈63% at a current density of 150 mA cm-2 on 2F-Cu-BDC derived catalyst is achieved. Using operando Raman measurements, it is revealed that the MOF derives to Cu2 O during eCO2 RR but organic linkers are stable. The fluorine group in organic linker can promote the H2 O dissociation to *H species, further facilitating the hydrogenation of *CO to *CHO that helps CC coupling.

Super-Coordinated Nickel N4 Ni1 O2 Site Single-Atom Catalyst for Selective H2 O2 Electrosynthesis at High Current Densities.

Electrochemical production of hydrogen peroxide (H2 O2 ) from O2 on single-atom catalysts has attracted great attention, yet the quest for robust catalysts is driven by achieving >90 % Faradaic efficiency (FE) under industrial-relevant current densities (>100 mA cm-2 ). Herein we synthesize a catalyst that contains single nickel site coordinated by four nitrogen and two oxygen atoms (i.e., N4 Ni1 O2 ) via involving carboxyl functionalized multiwall carbon nanotubes as a substrate to provide extra O coordination to the regular NiN4 site. It has a cathodic energy efficiency of approximately 82 % and a H2 O2 FE of around 96 % at 200 mA cm-2 current density, outperforming the reported single-atom catalysts for H2 O2 electrosynthesis.

BiPO4 -Derived 2D Nanosheets for Efficient Electrocatalytic Reduction of CO2 to Liquid Fuel.

The electrochemical reduction of carbon dioxide (CO2 ) to high-value liquid fuel with high selectivity is appealing for energy conversion and storage. Here we report a bismuth phosphate (BiPO4 ) derived 2D nanosheet-like electrocatalyst that efficiently converts CO2 into liquid-phase formate. The catalyst presents a formate Faradaic efficiency of over 90 % and a cathodic energy efficiency of 73 % at an industrially relevant current density of 200 mA cm-2 in the flow cell. The in situ generation of the Bi-O active species on the catalyst surface was determined via operando Raman measurement. Morphological and X-ray photoelectron spectroscopy analyses reveal the origin of the high activity for the electrosynthesis of formate from CO2 and water: the 2D structure together with the abundant insertion of oxygen atoms in the surface of the BiPO4 -derived nanosheets.

High-Dimensional Nb2O5 with NbO6 Octahedra for Efficient Electrocatalytic Upgrading of Methanol to Formate.

Facilitating the selective electrochemical oxidation of methanol into value-added formate is essential for electrochemical refining. Here we propose a high-dimensional Nb2O5 on Ni foam (Nb2O5-HD@NF) composite as anode for methanol oxidation reaction (MOR) for efficient production of formate. In an electrolyte containing 3 M methanol aqueous solution, the Nb2O5-HD@NF anode requires only 240 mV overpotential to deliver an industrial-level current density of 100 mA cm-2 with a formate Faraday efficiency of 100%. In situ Raman and electrochemical kinetic analyses reveal that the origin of the excellent activity in 3 M methanol electrolyte can be ascribed to the NbO6 octahedra as active sites and the Lewis acid sites on the surface of Nb2O5-HD. This work may pave a way for the design of non-noble metal electrocatalysts with surface acidity engineering for the effective electrocatalytic upgrading of biomass molecules.

Boosting nucleophilic attack to realize high current density biomass valorization on a tunable Prussian blue analogue.

Electrochemical biomass valorization provides a promising approach to generating value-added chemicals. Herein, we have creatively utilized a Prussian blue analogue as a structure template of the anodic catalyst and improved its catalyst capacity by adjusting its electronic structure. The nickel-based Prussian blue analogue/Ni foam (NiFe-PBA/NF) exhibits excellent performance for methanol (MeOH) oxidation and achieves almost 94.1% FE of formic acid at a high current density of 500 mA cm-2. Apart from formic acid, NiFe-PBA/NF also has good catalytic ability for ethanol, glycerol, glucose, and 5-hydroxymethylfurfural (HMF). In short, this work has developed a promising class of catalysts for biomass valorization.