Growing global energy demands and climate change motivate the development of new renewable energy technologies. In this context, water splitting using sustainable energy sources has emerged as an attractive process for carbon-neutral fuel cycles. A key scientific challenge to achieving this overall goal is the invention of new catalysts for the reductive and oxidative conversions of water to hydrogen and oxygen, respectively. This review article will highlight progress in molecular electrochemical approaches for catalytic reduction of protons to hydrogen, focusing on complexes of earth-abundant metals that can function in pure aqueous or mixed aqueous–organic media. The use of water as a reaction medium has dual benefits of maintaining high substrate concentration as well as minimizing the environmental impact from organic additives and by-products.

Complexes of earth-abundant metals for catalytic electrochemical hydrogen generation under aqueous conditions

Molecular catalysis plays an essential role in both natural and artificial photosynthesis (AP). However, the field of molecular catalysis for AP has gradually declined in recent years because of doubt about the long-term stability of molecular-catalyst-based devices. This review summarizes the development history of molecular-catalyst-based AP, including the fundamentals of AP, molecular catalysts for water oxidation, proton reduction and CO2 reduction, and molecular-catalyst-based AP devices, and it provides an analysis of the advantages, challenges, and stability of molecular catalysts. With this review, we aim to highlight the following points: (i) an investigation on molecular catalysis is one of the most promising ways to obtain atom-efficient catalysts with outstanding intrinsic activities; (ii) effective heterogenization of molecular catalysts is currently the primary challenge for the application of molecular catalysis in AP devices; (iii) development of molecular catalysts is a promising way to solve the problems of catalysis involved in practical solar fuel production. In molecular-catalysis-based AP, much has been attained, but more challenges remain with regard to long-term stability and heterogenization techniques.

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Artificial photosynthesis: opportunities and challenges of molecular catalysts

The synthesis of renewable fuels from abundant water or the greenhouse gas CO2 is a major step toward creating sustainable and scalable energy storage technologies. In the last few decades, much attention has focused on the development of nonprecious metal-based catalysts and, in more recent years, their integration in solid-state support materials and devices that operate in water. This review surveys the literature on 3d metal-based molecular catalysts and focuses on their immobilization on heterogeneous solid-state supports for electro-, photo-, and photoelectrocatalytic synthesis of fuels in aqueous media. The first sections highlight benchmark homogeneous systems using proton and CO2 reducing 3d transition metal catalysts as well as commonly employed methods for catalyst immobilization, including a discussion of supporting materials and anchoring groups. The subsequent sections elaborate on productive associations between molecular catalysts and a wide range of substrates based on carbon, quantum dot...

Electro- and Solar-Driven Fuel Synthesis with First Row Transition Metal Complexes.

A cobalt-sulfide (Co-S) film prepared via electrochemical deposition on conductive substrates is shown to behave as an efficient and robust catalyst for electrochemical and photoelectrochemical hydrogen generation from neutral pH water. Electrochemical experiments demonstrate that the film exhibits a low catalytic onset overpotential (η) of 43 mV, a Tafel slope of 93 mV/dec, and near 100% Faradaic efficiency in pH 7 phosphate buffer. Catalytic current densities can approach 50 mA/cm(2) and activity is maintained for at least 40 h. The catalyst can also be electrochemically coated on silicon, rendering a water-compatible photoelectrochemical system for hydrogen production under simulated 1 sun illumination. The facile preparation of this Co-S film, along with its low overpotential, high activity, and long-term aqueous stability, offer promising features for potential use in solar energy applications.

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Electrodeposited cobalt-sulfide catalyst for electrochemical and photoelectrochemical hydrogen generation from water.

A molecular proton reduction catalyst [FeFe](dcbdt)(CO)6 (1, dcbdt = 1,4-dicarboxylbenzene-2,3-dithiolate) with structural similarities to [FeFe]-hydrogenase active sites has been incorporated into a highly robust Zr(IV)-based metal-organic framework (MOF) by postsynthetic exchange (PSE). The PSE protocol is crucial as direct solvothermal synthesis fails to produce the functionalized MOF. The molecular integrity of the organometallic site within the MOF is demonstrated by a variety of techniques, including X-ray absorption spectroscopy. In conjunction with [Ru(bpy)3](2+) as a photosensitizer and ascorbate as an electron donor, MOF-[FeFe](dcbdt)(CO)6 catalyzes photochemical hydrogen evolution in water at pH 5. The immobilized catalyst shows substantially improved initial rates and overall hydrogen production when compared to a reference system of complex 1 in solution. Improved catalytic performance is ascribed to structural stabilization of the complex when incorporated in the MOF as well as the protection of reduced catalysts 1(-) and 1(2-) from undesirable charge recombination with oxidized ascorbate.

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Enhanced Photochemical Hydrogen Production by a Molecular Diiron Catalyst Incorporated into a Metal–Organic Framework

Electrocatalytic and photocatalytic hydrogen production in aqueous solution by a molecular cobalt complex.

A detailed examination of each step of the reaction sequence in the photochemical sacrificial hydrogen generation system consisting of [Ru(bpy)3]2+/ascorbate/[Co(DPA-bpy)OH2]3+ was conducted. By clearly defining quenching, charge separation, and back electron transfer in the [Ru(bpy)3]2+/ascorbate system, the details necessary for evaluation of the efficiency of water reduction with various catalysts are provided. In the particular Co(III) catalyst investigated, it is clear that the light induced catalytic process is considerably less efficient than the electrocatalytic process. A potential source of catalyst inefficiency in this system is reduction of the products formed in oxidation of the sacrificial electron donor. The data provided for excited state quenching and charge separation in this particular aqueous system are meant to be used by others for thorough investigation of the quantum efficiencies of other aqueous homogeneous and nanoheterogeneous catalysts for water reduction.

Mechanistic Details for Cobalt Catalyzed Photochemical Hydrogen Production in Aqueous Solution: Efficiencies of the Photochemical and Non-Photochemical Steps

Strategic preparation of porous magnetic molecularly imprinted polymers via a simple and green method for high-performance adsorption and removal of meropenem.

Xuan Anh N. Ma

Papers

Electrocatalytic and photocatalytic hydrogen production in aqueous solution by a molecular cobalt complex.

Mechanistic Details for Cobalt Catalyzed Photochemical Hydrogen Production in Aqueous Solution: Efficiencies of the Photochemical and Non-Photochemical Steps

Strategic preparation of porous magnetic molecularly imprinted polymers via a simple and green method for high-performance adsorption and removal of meropenem.