An effective cocatalyst is crucial for enhancing the visible photocatalytic performance of the hydrogen generation reaction. By using density-functional theory (DFT) and frontier molecular orbital (FMO) theory calculation analysis, the hydrogen adsorption free energy (ΔGH) of Ni-Mo alloy (458 kJ·mol(-1)) is found to be lower than that of Ni itself (537 kJ·mol(-1)). Inspired by these results, the novel, highly efficient cocatalyst NiMo@MIL-101 for photocatalysis of the hydrogen evolution reaction (HER) was fabricated using the double solvents method (DSM). In contrast with Ni@MIL-101 and Mo@MIL-101, NiMo@MIL-101 exhibited an excellent photocatalytic performance (740.2 μmol·h(-1) for HER), stability, and high apparent quantum efficiency (75.7%) under 520 nm illumination at pH 7. The NiMo@MIL-101 catalyst also showed a higher transient photocurrent, lower overpotential (-0.51 V), and longer fluorescence lifetime (1.57 ns). The results uncover the dependence of the photocatalytic activity of HER on the ΔGH of Ni-Mo (MoNi4) alloy nanoclusters, i.e., lower ΔGH corresponding to higher HER activity for the first time. The NiMo@MIL-101 catalyst could be a promising candidate to replace precious-metal catalysts of the HER.
The early mechanical performances of low-calcium fly ash (FFA)-based geopolymer (FFA–GEO) mortar can be enhanced by soda residue (SR). However, the resistance of SR–FFA–GEO mortar to acid or sulfate environments is unclear, owing to the various inorganic calcium salts in SR. The aim of this study was to investigate the long-term mechanical strengths of up to 360 d and evaluate the resistance of SR–FFA–GEO mortar to 5% HCl and 5% Na2SO4 environments through the losses in compressive strength and mass. Scanning Electron Microscopy (SEM), Energy-Dispersive Spectroscopy (EDS) and Fourier Transform Infrared Spectrometer (FTIR) experiments were conducted for the SR–FFA–GEO mortars, both before and after chemical attack, to clarify the attack mechanism. The results show that the resistances of the SR–FFA–GEO mortar with 20% SR (namely M10) to 5% HCl and 5% Na2SO4 environments are superior to those of cement mortar. The environmental HCl reacts with the calcites in SR to produce CaCl2, CO2 and H2O to form more pores under HCl attack, and the environmental Na+ cations from Na2SO4 go into Si-O-Al network structure, to further enhance the strength of mortar under Na2SO4 attack. These results provide the experimental basis for the durability optimization of SR–FFA–GEO mortars.
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