Electrocatalytic hydrogenation of acetonitrile to ethylamine in acid.

Electrochemical hydrogenation of acetonitrile based on well-developed proton exchange membrane electrolyzers holds great promise for practical production of ethylamine. However, the local acidic condition of proton exchange membrane results in severe competitive proton reduction reaction and poor selection toward acetonitrile hydrogenation. Herein, we conduct a systematic study to screen various metallic catalysts and discover Pd/C exhibits a 43.8% ethylamine Faradaic efficiency at the current density of 200 mA cm-2 with a specific production rate of 2912.5 mmol g-1 h-1, which is about an order of magnitude higher than the other screened metal catalysts. Operando characterizations indicate the in-situ formed PdHx is the active centers for catalytic reaction and the adsorption strength of the *MeCH2NH2 intermediate dictates the catalytic selectivity. More importantly, the theoretical analysis reveals a classic d-band mediated volcano curve to describe the relation between the electronic structures of catalysts and activity, which could provide valuable insights for designing more effective catalysts for electrochemical hydrogenation reactions and beyond.

Universal Synthesis of Amorphous Metal Oxide Nanomeshes.

Constructing the pore structures in amorphous metal oxide nanosheets can enhance their electrocatalytic performance by efficiently increasing specific surface areas and facilitating mass transport in electrocatalysis. However, the accurate synthesis for porous amorphous metal oxide nanosheets remains a challenge. Herein, a facile nitrate-assisted oxidation strategy is reported for synthesizing amorphous mesoporous iridium oxide nanomeshes (a-m IrOx NMs) with a pore size of ∼4 nm. X-ray absorption characterizations indicate that a-m IrOx NMs possess stretched Ir─O bonds and weaker Ir-O interaction compared with commercial IrO2. Combining thermogravimetric-fourier transform infrared spectroscopy with differential scanning calorimetry measurements, it is demonstrated that sodium nitrate, acting as an oxidizing agent, is conducive to the formation of amorphous nanosheets, while the NO2 produced by the in situ decomposition of nitrates facilitates the generation of pores within the nanomeshes. As an anode electrocatalyst in proton exchange membrane water electrolyzer, a-m IrOx NMs exhibit superior performance, maintaining a cell voltage of 1.67 V at 1 A cm-2 for 120 h without obvious decay with a low loading (0.4 mgcatalyst cm-2). Furthermore, the nitrate-assisted method is demonstrated to be a general approach to prepare various amorphous metal oxide nanomeshes, including amorphous RhOx, TiOx, ZrOx, AlOx, and HfOx nanomeshes.

Unveiling the nature of Pt-induced anti-deactivation of Ru for alkaline hydrogen oxidation reaction.

While Ru owns superior catalytic activity toward hydrogen oxidation reaction and cost advantages, the catalyst deactivation under high anodic potential range severely limits its potential to replace the Pt benchmark catalyst. Unveiling the deactivation mechanism of Ru and correspondingly developing protection strategies remain a great challenge. Herein, we develop atomic Pt-functioned Ru nanoparticles with excellent anti-deactivation feature and meanwhile employ advanced operando characterization tools to probe the underlying roles of Pt in the anti-deactivation. Our studies reveal the introduced Pt single atoms effectively prevent Ru from oxidative passivation and consequently preserve the interfacial water network for the critical H* oxidative release during catalysis. Clearly understanding the deactivation nature of Ru and Pt-induced anti-deactivation under atomic levels could provide valuable insights for rationally designing stable Ru-based catalysts for hydrogen oxidation reaction and beyond.

Lattice oxygen-mediated electron tuning promotes electrochemical hydrogenation of acetonitrile on copper catalysts.

Copper is well-known to be selective to primary amines via electrocatalytic nitriles hydrogenation. However, the correlation between the local fine structure and catalytic selectivity is still illusive. Herein, we find that residual lattice oxygen in oxide-derived Cu nanowires (OD-Cu NWs) plays vital roles in boosting the acetonitrile electroreduction efficiency. Especially at high current densities of more than 1.0 A cm-2, OD-Cu NWs exhibit relatively high Faradic efficiency. Meanwhile, a series of advanced in situ characterizations and theoretical calculations uncover that oxygen residues, in the form of Cu4-O configuration, act as electron acceptors to confine the free electron flow on the Cu surface, consequently improving the kinetics of nitriles hydrogenation catalysis. This work could provide new opportunities to further improve the hydrogenation performance of nitriles and beyond, by employing lattice oxygen-mediated electron tuning engineering.

Regulating Surface Reaction Kinetics through Ligand Field Effects for Fast and Reversible Aqueous Zinc Batteries.

Designing water-deficient solvation sheath of Zn2+ by ligand substitution is a widely used strategy to protect Zn metal anode, yet the intrinsic tradeoff between Zn nucleation/dissolution kinetics and the side hydrogen evolution reaction (HER) remains a huge challenge. Herein, we find boric acid (BA) with moderate ligand field interaction can partially replace H2 O molecules in the solvation sheath of Zn2+ , forming a stable water-deficient solvation sheath. It enables fast Zn nucleation/dissolution kinetics and substantially suppressed HER. Crucially, by systematically comparing the ligand field strength and solvation energies between BA and the ever-reported electrolyte additives, we also find that the solvation energy has a strong correlation with Zn nucleation/dissolution kinetics and HER inhibition ability, displaying a classic volcano behavior. The modulation map could provide valuable insights for solvation sheath design of zinc batteries and beyond.