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The application of catalytic hydro-dehalogenation is fundamentally constrained by its insufficient hydrogen activation sites. To address these limitations, an alloyed catalyst of ZVI-SiWRu was engineered via mechanochemical assembly of Ru nanoparticles and silicotungstic acid (H 4 SiW 12 O 40, SiW) onto micron-scale ZVI. The optimized catalyst demonstrated enhanced hydro-dehalogenation performance for trichloroethylene (TCE), achieving a faster degradation rate than conventional ZVI-Ru systems ( k obs = 4.08 h –1 vs 0.048 h –1 ), and exhibited high dechlorination capacity in saturated TCE levels (13.156 mmol/g/d). Combining in situ FTIR spectroscopy with DFT calculations revealed that electron-deficient tungsten (W) formed a ZVI-W interface, inducing an upward shift in the d-band center of ZVI (0.49 eV) to enhance electron delocalization. This optimized electronic structure boosted proton activation at ruthenium (Ru) sites, thereby reversing proton-deficiency-induced terminal carbon cleavage at Ru sites (reduced dehalogenation byproduct formation). More importantly, the proton affinity of tungsten enhanced proton spillover from Ru to the ZVI-W interface, synergistically inducing dual proton reservoirs (Ru hydride for hydrogen activation and SiW for proton relay) for deep dehalogenation and long-term durability (over 30 cycles). This work establishes a strategy for flexibly modulating the electronic structure in ruthenium to govern the activation behavior of carbon–halogen bonds, advancing solutions for organohalide remediation.
Yang et al. (Wed,) studied this question.