Efficient Visible Light-Driven Splitting of Alcohols into Hydrogen and Corresponding Carbonyl Compounds over a Ni-Modified CdS Photocatalyst

Abstract

Splitting of alcohols into hydrogen and corresponding carbonyl compounds has potential applications in hydrogen production and chemical industry. Herein, we report that a heterogeneous photocatalyst (Ni-modified CdS nanoparticles) could efficiently split alcohols into hydrogen and corresponding aldehydes or ketones in a stoichiometric manner under visible light irradiation. Optimized apparent quantum yields of 38%, 46%, and 48% were obtained at 447 nm for dehydrogenation of methanol, ethanol, and 2-propanol, respectively. In the case of dehydrogenation of 2-propanol, a turnover number of greater than 44 000 was achieved. To our knowledge, these are unprecedented values for photocatalytic splitting of liquid alcohols under visible light to date. Besides, the current catalyst system functions well with other aliphatic and aromatic alcohols, affording the corresponding carbonyl compounds with good to excellent conversion and outstanding selectivity. Moreover, mechanistic investigations suggest that an interface between Ni nanocrystal and CdS plays a key role in the reaction mechanism of the photocatalytic splitting of alcohol.

PdPt Alloy Nanocatalysts Supported on TiO2: Maneuvering Metal–Hydrogen Interactions for Light‐Driven and Water‐Donating Selective Alkyne Semihydrogenation

“…To minimize power consumption, photocatalysis is a promising approach to replace the conventional thermal process by solar energy in which the photogenerated electrons and holes can participate in organic reactions through various mechanisms . Meanwhile, the potential danger of explosion from high‐pressure H 2 can be avoided through catalytic hydrogen transfer in hydrogenation .…”

Photocatalysis with Quantum Dots and Visible Light for Effective Organic Synthesis

“…The generality of reaction was established by investigating over two‐dozen substituted benzyl alcohols, heterocyclic substituted alcohols, and α‐alkylated benzyl alcohols. Xu and co‐workers also reported a photocatalytic oxidation of alcohols using Ni‐modified CdS nanoparticles as photocatalysts under visible light irradiation . Both aliphatic and aromatic alcohols were converted into corresponding carbonyl compounds with a high selectivity and along with the evolution of hydrogen under mild conditions.…”

“…Xu and co-workersa lso reported ap hotocatalytic oxidation of alcohols using Ni-modified CdS nanoparticles as photocatalysts under visible light irradiation. [24] Both aliphatic and aromatic alcohols were converted into corresponding carbonyl compounds with ah igh selectivity and along with the evolution of hydrogen under mild conditions.…”

Metal‐ and Additive‐Free Oxidation of Sulfides into Sulfoxides by Fullerene‐Modified Carbon Nitride with Visible‐Light Illumination

“…Furthermore, the reactions were conducted in different solvents to study its influence on the photocatalytic oxidation of 1a (Table 2). Interestingly,t he solventh ad ag reat effect on the photocatalytic activity of the 4wt% C 60 /g-C 3 N 4 catalyst towards the oxidation of 1a.N or eaction took place in THF ( Table 2, entry 1), and the reactions in ethanol and benzotrifluoride produced low conversionso f2 2.5 and 30.4 %( Ta ble 2, entries 2 and 3), respectively.A cetonitrile is considered to be the best solventf or photocatalytic reactions in some cases, [36,37] and it also produced ah igh conversion of 83.9 %( Ta ble 2, entry 4); however,t he selectivity of methyl phenyl sulfoxide (1b)w as poor.I th as been reported that Pt/BiVO 4 systems exhibit excel- [a] Reactionc onditions: 1a (0.2 mmol), 4wt% C 60 /g-C 3 N 4 (30 mg), solvent (5 mL), oxygenb alloon,r oom temperature, Xe lamp (1 Wcm À2 , l > 400 nm). ChemSusChem 2018ChemSusChem , 11,2444ChemSusChem -2452 www.chemsuschem.org lent performance fort he oxidation of sulfides in water,c ompared with in organic solvents.…”