Surfactants Used in Colloidal Synthesis Modulate Ni Nanoparticle Surface Evolution for Selective CO2 Hydrogenation.

Colloidal chemistry holds promise to prepare uniform and size-controllable pre-catalysts; however, it remains a challenge to unveil the atomic-level transition from pre-catalysts to active catalytic surfaces under the reaction conditions to enable the mechanistic design of catalysts. Here, we report an ambient-pressure X-ray photoelectron spectroscopy study, coupled with in situ environmental transmission electron microscopy, infrared spectroscopy, and theoretical calculations, to elucidate the surface catalytic sites of colloidal Ni nanoparticles for CO2 hydrogenation. We show that Ni nanoparticles with phosphine ligands exhibit a distinct surface evolution compared with amine-capped ones, owing to the diffusion of P under oxidative (air) or reductive (CO2 + H2) gaseous environments at elevated temperatures. The resulting NiPx surface leads to a substantially improved selectivity for CO production, in contrast to the metallic Ni, which favors CH4. The further elimination of surface metallic Ni sites by designing multi-step P incorporation achieves unit selectivity of CO in high-rate CO2 hydrogenation.

Non-iridium-based electrocatalyst for durable acidic oxygen evolution reaction in proton exchange membrane water electrolysis.

Iridium-based electrocatalysts remain the only practical anode catalysts for proton exchange membrane (PEM) water electrolysis, due to their excellent stability under acidic oxygen evolution reaction (OER), but are greatly limited by their high cost and low reserves. Here, we report a nickel-stabilized, ruthenium dioxide (Ni-RuO2) catalyst, a promising alternative to iridium, with high activity and durability in acidic OER for PEM water electrolysis. While pristine RuO2 showed poor acidic OER stability and degraded within a short period of continuous operation, the incorporation of Ni greatly stabilized the RuO2 lattice and extended its durability by more than one order of magnitude. When applied to the anode of a PEM water electrolyser, our Ni-RuO2 catalyst demonstrated >1,000 h stability under a water-splitting current of 200 mA cm-2, suggesting potential for practical applications. Density functional theory studies, coupled with operando differential electrochemical mass spectroscopy analysis, confirmed the adsorbate-evolving mechanism on Ni-RuO2, as well as the critical role of Ni dopants in stabilization of surface Ru and subsurface oxygen for improved OER durability.

Hybrid Catalyst Coupling Single-Atom Ni and Nanoscale Cu for Efficient CO2 Electroreduction to Ethylene.

A hybrid catalyst with integrated single-atom Ni and nanoscale Cu catalytic components is reported to enhance the C-C coupling and ethylene (C2H4) production efficiency in the electrocatalytic CO2 reduction reaction (eCO2RR). The single-atom Ni anchored on high-surface-area ordered mesoporous carbon enables high-rate and selective conversion of CO2 to CO in a wide potential range, which complements the subsequent CO enrichment on Cu nanowires (NWs) for the C-C coupling to C2H4. In situ surface-enhanced infrared absorption spectroscopy (SEIRAS) confirms the substantially improved CO enrichment on Cu, once the incorporation of single-atom Ni occurs. Also, in situ X-ray absorption near-edge structure (XANES) demonstrates the structural stability of the hybrid catalyst during eCO2RR. By modulating hybrid compositions, the optimized catalyst shows 66% Faradaic efficiency (FE) in an alkaline flow cell with over 100 mA·cm-2 at -0.5 V versus reversible hydrogen electrode, leading to a five-order enhancement in C2H4 selectivity compared with single-component Cu NWs.

Effect of support on the performance of PtRu-based catalysts in oxidative steam reforming of ethanol to produce hydrogen.

Oxidative steam reforming of ethanol (OSRE) to produce hydrogen has been investigated over a series of supported PtRu catalysts, with different supports. Bimetallic PtRu-based catalysts were prepared by the impregnation method using H2PtCl6 and RuCl3 as precursors. Six supports (reducible oxides of ZrO2, CeO2, and Co3O4, and irreducible oxides of ZnO, Al2O3, and NiO) were chosen to fabricate bimetallic catalysts. The catalytic performance of the OSRE reaction in the series of PtRu-based samples was evaluated using a fixed-bed flow reactor under atmospheric pressure. In front reaction, the catalyst was pre-activated by reduction under 200°C for 3 h. The gas hourly space velocity was adjusted at 66,000 h-1, and the optimal molar ratios of the H2O/EtOH and O2/EtOH feeds were 4.9 and 0.44, respectively. The results indicated that the PtRu supported on the ZrO2 and CeO2 exhibited superior catalytic performance in the OSRE reaction under a low temperature (a TR of approximately 320°C) for producing the main products of H2 and CO2 with lower CO and CH4 by-products. Also, it was quite stable during a long time evaluation; the maximum YH2 maintained at 4.5-4.2, and the CO distribution approached 3.3-3.5 mol% around 84 h test at 340°C over the PtRu/ZrO2 catalyst.