Transition metal carbides (TMCs) feature high catalytic activity and superior stability for the hydrogen evolution reaction (HER). However, their platinum‐like HER catalytic performance is heavily hindered, due to their strong interaction with hydrogen. Herein, Ni activation of TMCs (M = V, Fe, Cr, and Mo) is proposed through introducing adsorbed nickel atoms on the TMC surface (Ni/TMC). In both acidic and alkaline solutions, a sharp decrease of both overpotentials and Tafel slopes of the Ni/TMC catalysts for HER is achieved. At 10 mA cm−2, the overpotentials of the Ni/vanadium carbide (VC) and Ni/Fe3C catalysts are 128 and 93 mV in 1 m KOH, 111 and 112 mV in 0.5 m H2SO4, respectively. Even at 150 mA cm−2, they exhibit the overpotentials of as low as 270 and 291 mV, respectively. In the alkaline solutions, the performance of these Ni/TMC catalysts is even superior to a Pt/C catalyst. As confirmed from density functional theory calculations and X‐ray absorption fine structure analysis, such adsorbed Ni atoms effectively optimize the d‐electron structure and improve HER performance. As a versatile strategy, this work provides a universal route to activate TMCs for highly efficient HER in different media.

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Surface self‐reconstruction via incorporating an amorphous structure on the surface of a catalyst can induce abundant defects and unsaturated sites for enhanced hydrogen evolution reaction (HER) activity. Herein, an electrochemical activation method is proposed to reconstruct the surface of a Cu‐Fe3O4 catalyst. Following a “dissolution–redeposition” path, the defective FeOOH is formed under potential stimulation on the surface of the Cu‐Fe3O4 precursor during the electrochemical activation process. This Cu‐FeOOH/Fe3O4 catalyst exhibits excellent stability as well as extremely low overpotential toward the alkaline HER (e.g., 129 and 285 mV at the large current densities of −100 and 500 mA cm−2, respectively), much superior to the Pt/C catalyst. The experimental and density functional theory calculation results demonstrate that the Cu‐FeOOH/Fe3O4 catalyst has abundant oxygen vacancies, featuring optimized surface chemical composition and electronic structure for improving the active sites and intrinsic activity. Introducing defective FeOOH on the surface of a Cu‐Fe3O4 catalyst by means of an electrochemical activation method decreases the energy barrier of both H2O dissociation and H2 generation. Such a surface self‐reconstruction strategy provides a new avenue toward the production of efficient non‐noble metal catalysts for the HER.

The use of Fe Fischer−Tropsch (F−T) catalysts in slurry bubble column reactors (SBCRs) has been problematic in the past because of their poor attrition resistance. Recently, we have reported the preparation of spray-dried Fe F−T catalysts having attrition resistance suitable for SBCR use, but the reason for this improvement was not clear. This paper focuses on research done to better understand the reason for the high attrition resistance of some of the Fe catalysts prepared. Understanding the relationship between the catalyst attrition resistance and composition/structure is important for the preparation of attrition-resistant Fe catalysts. In the present study, two series of spray-dried Fe F−T catalysts having the composition Fe/Cu/K/SiO2 but with different amounts of precipitated and/or binder SiO2 were investigated. All of the catalysts studied were evaluated in their calcined form. This was done to minimize any possible attrition due to Fe phase change (such as can occur during activation and F−T synthesis) in order to address the effect of the other catalyst properties. A companion paper addresses attrition due to phase change after carburization. It was found that particle density, principally among other particle properties of the catalysts, correlated with the intrinsic catalyst attrition resistance. Changes in fluidization in the jet cup attrition test with changes in particle density only had minimal effects on the results. Particle density differences reflected differences in the catalyst inner structure. Differences in SiO2 type and concentration resulted in different structures for the SiO2 network and therefore affected the catalyst structure.