Self-Protonated Ho-Doped Zn(O,S) as a Green Chemical-Conversion Catalyst to Hydrogenate Nitro to Amino Compounds.

Zn(O,S) has been successfully doped with different amounts of Ho and characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), electrochemical impedance spectroscopy (EIS), and transient photocurrent (TPC). The as-prepared Ho-doped Zn(O,S) catalysts with different Ho amounts are evaluated for hydrogen evolution reaction. The catalyst with the best performance in evolving hydrogen is further utilized to hydrogenate 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). It is found that doping with Ho obviously enhanced charge transfer and photoresponse properties of the catalyst. Therefore, the modified Zn(O,S) can optimally evolve hydrogen by 18 624 µmol/g, which is 20% higher than that of pristine Zn(O,S). Subsequently, the in situ generated hydrogen ions on catalyst surfaces also play an important role as a hydrogen source to hydrogenate 4-NP to 4-AP without any reducing agents such as NaBH4, which is commonly used as a hydrogen source. As Ho is doped in the lattices of Zn(O,S), it acts not only to separate photocarriers and to enhance the charge transfer but also to shorten the diffusion time of nitrophenolate ions to catalyst surfaces for further photocatalytic hydrogenation reaction (PHR) process. A plausible PHR mechanism has been provided to elucidate the great performance of Ho-modified Zn(O,S) for photocatalytic hydrogenation.