The development of highly active, universal, and stable inexpensive electrocatalysts/cocatalysts for hydrogen evolution reaction (HER) by morphology and structure modulations remains a great challenge. Herein, a simple self-template strategy was developed to synthesize hollow Co-based bimetallic sulfide (MxCo3-xS4, M = Zn, Ni, and Cu) polyhedra with superior HER activity and stability. Homogenous bimetallic metal-organic frameworks are transformed to hollow bimetallic sulfides by solvothermal sulfidation and thermal annealing. Electrochemical measurements and density functional theory computations show that the combination of hollow structure and homoincorporation of a second metal significantly enhances the HER activity of Co3S4. Specifically, the homogeneous doping in Co3S4 lattice optimizes the Gibbs free energy for H* adsorption and improves the electrical conductivity. Impressively, hollow Zn0.30Co2.70S4 exhibits electrocatalytic HER activity better than most of the reported nobel-metal-free electrocatalysts over a wide pH range, with overpotentials of 80, 90, and 85 mV at 10 mA cm(-2) and 129, 144, and 136 mV at 100 mA cm(-2) in 0.5 M H2SO4, 0.1 M phosphate buffer, and 1 M KOH, respectively. It also exhibits photocatalytic HER activity comparable to that of Pt cocatalyst when working with organic photosensitizer (Eosin Y) or semiconductors (TiO2 and C3N4). Furthermore, this catalyst shows excellent stability in the electrochemical and photocatalytic reactions. The strategy developed here, i.e., homogeneous doping and self-templated hollow structure, provides a way to synthesize transition metal sulfides for catalysis and energy conversion.

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The structural diversity of highly connected metal–organic frameworks (MOFs) has long been limited due to the scarcity of highly connected metal clusters and the corresponding available topology. Herein, we deliberately chose a series of tritopic linkers with multiple substituents to construct a series of highly connected rare-earth (RE) MOFs. The steric hindrance of these substituents can be systematically tuned to generate various linker rotamers with tunable configurations and symmetries. For example, the methyl-functionalized linker (L-CH3) with C 2v symmetry exhibits larger steric hindrance, forcing two peripheral phenyl rings perpendicular to the central one. The combination of C 2v linkers and 9-connected RE6 clusters leads to the formation of a new fascinating (3,9)-c sep topology. Unlike Zr-MOFs exhibiting Zr6 clusters in various linker configurations and corresponding different structures, the adaptable RE6 clusters can undergo metal insertion and rearrange into new RE9 clusters when connected to an unfunctionalized linker (L–H) with C 1 symmetry, giving rise to a new (3,3,18)-c ytw topology. More interestingly, by judiciously combining the linkers with both small and bulky substituents through mixed-linker strategies, an RE9-based MOF with an engaging (3,3,12)-c flg topology could be obtained as a result of continuous steric hindrance control. In this case, the two mixed linkers adopt configurations with moderate steric hindrances. Molecular simulation demonstrates that the combination of substituents with various steric hindrances dictates the resulting MOF structures. This work provides insights into the discovery of unprecedented topologies through systematic and continuous steric tuning, which can further serve as a blueprint for the design and construction of highly complicated porous structures for sophisticated applications.

We study a nonsingular bounce inflation model, which can drive the early universe from a contracting phase, bounce into an ordinary inflationary phase, followed by the reheating process. Besides the bounce that avoided the Big-Bang singularity which appears in the standard cosmological scenario, we make use of the Horndesky theory and design the kinetic and potential forms of the lagrangian, so that neither of the two big problems in bouncing cosmology, namely the ghost and the anisotropy problems, will appear. The cosmological perturbations can be generated either in the contracting phase or in the inflationary phase, where in the latter the power spectrum will be scale-invariant and fit the observational data, while in the former the perturbations will have nontrivial features that will be tested by the large scale structure experiments. We also fit our model to the CMB TT power spectrum.