Oxidation State Engineering in Octahedral Ni by Anchored Sulfate to Boost Intrinsic Oxygen Evolution Activity

Promoting the electron occupancy of active sites to unity is an effective method to enhance the oxygen evolution reaction (OER) performance of spinel oxides, but it remains a great challenge. Here, an in situ approach is developed to modify the valence state of octahedral Ni cations in NiFe2O4 inverse spinel via surface sulfates (SO42–). Different from previous studies, SO42– is directly anchored on the spinel surface instead of forming from uncontrolled conversion or surface reconstruction. Experiment and theoretical calculations reveal the precise adsorption sites and spatial arrangement for SO42– species. As a main promoting factor, surface SO42– effectively converts the crystal field stable Ni state (t2g6eg2) to the near-unity eg electron state (t2g6eg1). Moreover, the inevitable oxygen vacancies (Vo) further optimize the energy barrier of the potential-determining step (from OH* to O*). This co-modification strategy enhances turnover frequency-based electrocatalytic activity about two orders higher than the control sample without surface sulfates. This work may provide insight into the OER activity enhancement mechanism by the oxyanion groups

Size-Selective Catalytic Growth of Nearly 100% Pure Carbon Nanocoils with Copper Nanoparticles Produced by Atomic Layer Deposition

In this paper, Cu nanoparticles with narrow size distribution are synthesized by reduction of CuO films produced by atomic layer deposition (ALD), which are used as catalysts for the catalytic growth of carbon nanostructures. By properly adjusting the ALD cycle numbers, the size of produced Cu nanoparticles can be well controlled. Uniform carbon nanocoils with near 100% purity can be obtained by using 50–80 nm Cu nanoparticles, while thin straight fibers and thick straight fibers are produced by applying 5–35 and 100–200 nm Cu nanoparticles, respectively. The mechanism of the particle size-dependent growth of the carbon nanostructure was analyzed based on the experimental results and theoretical simulation. Our results can provide important information for the preparation of helical carbon nanostructures with high purity. Moreover, this work also demonstrates that ALD is a viable technique for synthesizing nanoparticles with highly controllable size and narrow size distribution suitable for studying particle size-dependent catalytic behavior and other applications