Ru nanoclusters anchored on boron- and nitrogen-doped carbon for a highly efficient hydrogen evolution reaction in alkaline seawater.

Electrochemical seawater splitting is an intriguing strategy for green hydrogen production. Constructing advanced electrocatalysts for the hydrogen evolution reaction (HER) in seawater is extremely demanded for accelerating the sluggish kinetic process. Herein, a Ru nanocluster anchored on boron- and nitrogen-doped carbon (Ru/NBC) catalyst was successfully synthesized for the HER in alkaline/seawater electrolytes. Remarkably, Ru/NBC exhibits outstanding activity and durability, delivering low overpotentials@10 mA cm-2 in 1.0 M KOH (30 mV) and 1.0 M KOH + seawater electrolyte (35 mV), outperforming Pt/C, Ru/NC, Ru/BC and Ru/C. Additionally, Ru/NBC also provides a high specific activity of 0.093 mA cm-2ECSA at an overpotential of 150 mV, which is higher than those of Ru/NC, Ru/BC and Ru/C, respectively. Density functional theory calculation results demonstrate that the Ru-B formed interfacial chemical bond can regulate the electronic structure of Ru active sites of Ru/NBC, which can facilitate the adsorption of water and hydrogen in alkaline media. This work provides a feasible strategy to fabricate outstanding electrocatalysts for the HER in alkaline/alkaline seawater electrolytes.

Highly Dispersed Ni Nanoparticles on Anhydrous Calcium Silicate (ACS) Nanosheets for Catalytic Dry Reforming of Methane: Tuning the Activity by Different Ways of Ni Introduction.

Three kinds of nickel-loaded anhydrous calcium silicate nanocatalysts (ACS), including Ni-ACS-Dop, Ni-ACS-Iex and Ni-ACS-Im, were prepared by introducing Ni species through doping in the synthesis of calcium silicate hydrate (CSH) nanosheets, ion-exchange with premade CSH nanosheets and deposition on calcined ACS nanosheets, respectively. Although Ni species were introduced in different ways, all the Ni-ACS catalysts showed similar chemical compositions and microstructures, where Ni nanoparticles were highly dispersed on the ultrathin ACS nanosheets with a large surface area and good thermal stability. However, the differences in the way of Ni introduction did produce Ni with different electronic states. The Ni-ACS-Iex catalyst with "surface Ni" as a dominant form had more electrons enriched on the surface of Ni, which led to the highest activity in the dry reforming of methane (DRM) reaction among the three catalysts, whereas the Ni-ACS-Dop catalyst with "lattice Ni" as a dominant form showed an electron-deficient property and lowest activity. Different from the introduction of a more favourable nanostructure or chemical component to the catalyst system, this work controlled the chemical environment of metal precursors and created metal catalysts with a preferred surface electronic state during synthesis, which could be a new strategy to improve the catalytic activity.

NixCoy Nanocatalyst Supported by ZrO2 Hollow Sphere for Dry Reforming of Methane: Synergetic Catalysis by Ni and Co in Alloy.

NixCoy/H-ZrO2 catalysts composed of highly dispersed NixCoy nanoparticles supported by mesoporous ZrO2 hollow sphere are synthesized by templating and impregnation processes. According to thermogravimetric analysis, X-ray photoelectron spectroscopy, and dry reforming results, a synergetic reaction mechanism is proposed to explain the better performance of alloy catalysts compared to Ni/H-ZrO2 or Co/H-ZrO2. In dry reforming of methane (DRM) reaction, Ni and Co act as catalysts for CH4 cracking and CO2 reduction, respectively, and the induced carbon deposits on Ni can be oxidized by the active oxygen left on Co, which regenerate the metal surface for the following reaction. Among all the alloy catalysts, the Ni0.8Co0.2/H-ZrO2 catalyst presents the highest activity and stability because the strong metal-support interaction prevents the sintering of nanocatalysts at high temperature and the hollow structure enhances the mass transportation of reactants and products. More importantly, Ni and Co can synergistically balance the speed of CH4 cracking and CO2 reduction, which effectively avoid coke accumulation/catalyst oxidation and ensure fast and stable conversion for DRM reaction.

Internally Supported Metal-Oxide Nanocatalyst for Hydrogenation of Nitroaromatics.

The uncalcined but highly dispersive oxide-supported metal catalyst for liquid phase reactions may suffer from the agglomeration of metal nanoparticles and the drop of metal catalyst in solution, which will decrease the activity and shorten their life in catalysis. Here, a one-pot successive polyol reaction was developed to prepare M-E xO y colloidal particles as heterogeneous nanocatalysts, which merge the controlled synthesis of metal catalysts and oxide supports, the in situ loading of catalyst, and even the mesopore amplification into a highly integrated process. Unlike the traditional surface-deposited catalysts, the noble metal nanoparticles even with a large amount of loading are internally dispersed in the mesoporous oxide particles, which show higher activity and stability in the hydrogenation of nitroaromatics compared to the isolated nanocatalysts or surface-deposited catalysts. The improved activity and stability comes from the physical confinement of metal nanoparticles and good mass transportation of substrate/product within the support particles. This work proposed a novel method to prepare highly dispersed metal catalysts, which could be potentially useful to heterogeneous catalytic reactions with high-throughput and long-life demands.