Lignocellulose is Earth's most abundant form of biomass and its valorisation to H 2 is a key objective for the generation of renewable fuels. Solar-driven photocatalytic reforming of lignocellulose to H 2 at ambient temperature offers a sustainable route towards this goal, but this reaction is currently limited to noble metal containing systems that operate with low activity under UV light. Here, we report the light-driven photoreforming of cellulose, hemicellulose and lignin to H 2 using semiconducting cadmium sulfide quantum dots in alkaline aqueous solution. We show that basic conditions cause these dots to become coated with oxide/hydroxide in situ, presenting a strategy to improve their photocatalytic performance. The system operates under visible light, is stable beyond 6 days and is even able to reform unprocessed lignocellulose, such as wood and paper, under solar irradiation at room temperature, presenting an inexpensive route to drive aqueous proton reduction to H 2 through waste biomass oxidation.

Plastic waste is recycled to hydrogen using sunlight and a CdS photocatalyst.

Photocatalytic conversion of CO into carbonaceous feedstock chemicals is a promising strategy to mitigate greenhouse gas emissions and simultaneously store solar energy in chemical form. Photocatalysts for this transformation are typically based on precious metals and operate in nonaqueous solvents to suppress competing H generation. In this work, we demonstrate selective visible-light-driven CO reduction in water using a synthetic photocatalyst system that is entirely free of precious metals. We present a series of self-assembled nickel terpyridine complexes as electrocatalysts for the reduction of CO to CO in organic media. Immobilization on CdS quantum dots allows these catalysts to be active in purely aqueous solution and photocatalytically reduce CO with >90% selectivity under UV-filtered simulated solar light irradiation (AM 1.5G, 100 mW cm, λ > 400 nm, pH 6.7, 25 °C). Correlation between catalyst immobilization efficiency and product selectivity shows that anchoring the molecular catalyst on the semiconductor surface is key in controlling the selectivity for CO reduction over H evolution in aqueous solution.

The development of high-performance electrocatalytic systems for the controlled reduction of CO2 to value-added chemicals is a key goal in emerging renewable energy technologies. The lack of selective and scalable catalysts in aqueous solution currently hampers the implementation of such a process. Here, the assembly of a [MnBr(2,2′-bipyridine)(CO)3] complex anchored to a carbon nanotube electrode via a pyrene unit is reported. Immobilization of the molecular catalyst allows electrocatalytic reduction of CO2 under fully aqueous conditions with a catalytic onset overpotential of η = 360 mV, and controlled potential electrolysis generated more than 1000 turnovers at η = 550 mV. The product selectivity can be tuned by alteration of the catalyst loading on the nanotube surface. CO was observed as the main product at high catalyst loadings, whereas formate was the dominant CO2 reduction product at low catalyst loadings. Using UV–vis and surface-sensitive IR spectroelectrochemical techniques, two different intermediates were identified as responsible for the change in selectivity of the heterogenized Mn catalyst. The formation of a dimeric Mn0 species at higher surface loading was shown to preferentially lead to CO formation, whereas at lower surface loading the electrochemical generation of a monomeric Mn-hydride is suggested to greatly enhance the production of formate. These results emphasize the advantages of integrating molecular catalysts onto electrode surfaces for enhancing catalytic activity while allowing excellent control and a deeper understanding of the catalytic mechanisms.