Amorphous alloys structurally deviate from crystalline materials in that they possess unique short-range ordered and long-range disordered atomic arrangement. They are important catalytic materials due to their unique chemical and structural properties including broadly adjustable composition, structural homogeneity, and high concentration of coordinatively unsaturated sites. As chemically reduced metal–metalloid amorphous alloys exhibit excellent catalytic performance in applications such as efficient chemical production, energy conversion, and environmental remediation, there is an intense surge in interest in using them as catalytic materials. This critical review summarizes the progress in the study of the metal–metalloid amorphous alloy catalysts, mainly in recent decades, with special focus on their synthetic strategies and catalytic applications in petrochemical, fine chemical, energy, and environmental relevant reactions. The review is intended to be a valuable resource to researchers interested in these exciting catalytic materials. We concluded the review with some perspectives on the challenges and opportunities about the future developments of metal–metalloid amorphous alloy catalysts.

It has been documented that W-modified Pt catalysts with relatively high tungsten contents are effective for the catalytic transformation of biodiesel-derived glycerol to 1,3-propanediol (1,3-PDO). Herein, we report a new finding that Pt/W–SBA-15 catalysts with extremely low W/Si atomic ratios (≤1/80) exhibit excellent catalytic performance in the hydrogenolysis of glycerol to 1,3-PDO. In particular, a Pt/W–SBA-15 catalyst with the W/Si ratio of as low as 1/640 (Pt/W–SBA-15(1/640)) gave rise to the highest 1,3-PDO selectivity of 70.8% at a high glycerol conversion of 86.8% and thus afforded the highest yield of 1,3-PDO of 61.5%. A combination of characterization techniques evidenced that tungsten was homogeneously incorporated into SBA-15 in the form of isolated tetragonal WO₄ and only displayed Lewis acidity. The particle size of Pt evolved in a reverse volcanic curve with the W/Si ratio, with the smallest size being observed for Pt/W–SBA-15(1/640). Control experiments indicated strong synergy between Pt nanoparticles (NPs) and WO₄ in the hydrogenolysis of glycerol. A probe reaction suggested that Brønsted acid sites were generated in situ on the Pt/W–SBA-15 catalysts in a H₂ atmosphere by the reaction between WO₄ and spillover H atoms from the Pt NPs. It is plausible that the hydrided WO₄ functioned as a highly selective active centre in the hydrogenolysis of glycerol to 1,3-PDO, whereas the Pt NPs played the role of a reservoir of spillover H atoms. Thus, a good match between the isolated WO₄ and the small Pt NPs was responsible for the superior catalytic performance of Pt/W–SBA-15(1/640).

A novel Raney Fe@HZSM-5 Fischer–Tropsch synthesis catalyst was synthesized via a facile one-pot strategy using an FeAl alloy as the Fe precursor and as the Al source. Aside from cracking/isomerization of heavy hydrocarbons, HZSM-5 also stabilizes Hägg carbide, resulting in excellent selectivity to gasoline fraction and unexpectedly enhanced C₅₊ selectivity.