Scalable and robust electrocatalysts are required for the implementation of water splitting technologies as a globally applicable means of producing affordable renewable hydrogen. It is demonstrated that iron-only electrode materials prove to be active for catalyzing both proton reduction and water oxidation in alkaline electrolyte solution with superior activity to that of previously established bi-functional catalysts containing less abundant elements. The reported bi-functionality of the iron electrodes is reversible upon switching of the applied bias through electrochemical interconversion of catalytic species at the electrode surface. Cycling of the applied bias results in in-situ electrochemical regeneration of the catalytic surfaces and thereby extends the catalyst stability and lifetime of the water electrolyzer. Full water splitting at a current density of I = 10 mA cm⁻² is achieved at a bias of ≈2 V, which is stable over at least 3 d (72 one hour switching cycles). Thus, potential-switching is established as a possible strategy of stabilizing electrode materials against degradation in symmetrical water splitting systems.

The combination of enzymes with semiconductors enables the photoelectrochemical characterization of electron-transfer processes at highly active and well-defined catalytic sites on a light-harvesting electrode surface. Herein, we report the integration of a hydrogenase on a TiO₂-coated p-Si photocathode for the photo-reduction of protons to H₂. The immobilized hydrogenase exhibits activity on Si attributable to a bifunctional TiO₂ layer, which protects the Si electrode from oxidation and acts as a biocompatible support layer for the productive adsorption of the enzyme. The p-Si|TiO₂|hydrogenase photocathode displays visible-light driven production of H₂ at an energy-storing, positive electrochemical potential and an essentially quantitative faradaic efficiency. We have thus established a widely applicable platform to wire redox enzymes in an active configuration on a p-type semiconductor photocathode through the engineering of the enzyme–materials interface.

A freestanding H₂-evolution electrode consisting of a copolymer-embedded cobaloxime integrated into a multiwall carbon nanotube matrix by π–π interactions is reported. This electrode is straightforward to assemble and displays high activity towards hydrogen evolution in near-neutral pH solution under inert and aerobic conditions, with a cobalt-based turnover number (TON_Co) of up to 420. An analogous electrode with a monomeric cobaloxime showed less activity with a TON_Co of only 80. These results suggest that, in addition to the high surface area of the porous network of the buckypaper, the polymeric scaffold provides a stabilizing environment to the catalyst, leading to further enhancement in catalytic performance. We have therefore established that the use of a multifunctional copolymeric architecture is a viable strategy to enhance the performance of molecular electrocatalysts.

The combination of enzymes with semiconductors enables the photoelectrochemical characterization of electron-transfer processes at highly active and well-defined catalytic sites on a light-harvesting electrode surface. Herein, we report the integration of a hydrogenase on a TiO₂-coated p-Si photocathode for the photo-reduction of protons to H₂. The immobilized hydrogenase exhibits activity on Si attributable to a bifunctional TiO₂ layer, which protects the Si electrode from oxidation and acts as a biocompatible support layer for the productive adsorption of the enzyme. The p-Si|TiO₂|hydrogenase photocathode displays visible-light driven production of H₂ at an energy-storing, positive electrochemical potential and an essentially quantitative faradaic efficiency. We have thus established a widely applicable platform to wire redox enzymes in an active configuration on a p-type semiconductor photocathode through the engineering of the enzyme–materials interface.

A freestanding H₂-evolution electrode consisting of a copolymer-embedded cobaloxime integrated into a multiwall carbon nanotube matrix by π–π interactions is reported. This electrode is straightforward to assemble and displays high activity towards hydrogen evolution in near-neutral pH solution under inert and aerobic conditions, with a cobalt-based turnover number (TON_Co) of up to 420. An analogous electrode with a monomeric cobaloxime showed less activity with a TON_Co of only 80. These results suggest that, in addition to the high surface area of the porous network of the buckypaper, the polymeric scaffold provides a stabilizing environment to the catalyst, leading to further enhancement in catalytic performance. We have therefore established that the use of a multifunctional copolymeric architecture is a viable strategy to enhance the performance of molecular electrocatalysts.

The straightforward and inexpensive fabrication of stabilized and activated photoelectrodes for application to tandem photoelectrochemical (PEC) water splitting is reported. Semiconductors such as Si, WO₃, and BiVO₄ can be coated with a composite layer formed upon hydrolytic decomposition of hetero­bimetallic single source precursors (SSPs) based on Ti and Ni, or Ti and Co in a simple single-step process under ambient conditions. The resulting 3d-transition metal oxide composite films are multifunctional, as they protect the semiconductor electrode from corrosion with an amorphous TiO₂ coating and act as bifunctional electrocatalysts for H₂ and O₂ evolution based on catalytic Ni or Co species. Thus, this approach enables the use of the same precursors for both photoelectrodes in tandem PEC water splitting, and SSP chemistry is thereby established as a highly versatile low-cost approach to protect and activate photoelectrodes. In an optimized system, SSP coating of a Si photocathode and a BiVO₄ photoanode resulted in a benchmark noble metal-free dual-photoelectrode tandem PEC cell for overall solar water splitting with an applied bias solar-to-hydrogen conversion efficiency of 0.59% and a half-life photostability of 5 h.

In nature, charge recombination in light-harvesting reaction centers is minimized by efficient charge separation. Here, it is aimed to mimic this by coupling dye-sensitized TiO₂ nanocrystals to a decaheme protein, MtrC from Shewanella oneidensis MR-1, where the 10 hemes of MtrC form a ≈7-nm-long molecular wire between the TiO₂ and the underlying electrode. The system is assembled by forming a densely packed MtrC film on an ultra-flat gold electrode, followed by the adsorption of approximately 7 nm TiO₂ nanocrystals that are modified with a phosphonated bipyridine Ru(II) dye (RuP). The step-by-step construction of the MtrC/TiO₂ system is monitored with (photo)electrochemistry, quartz-crystal microbalance with dissipation (QCM-D), and atomic force microscopy (AFM). Photocurrents are dependent on the redox state of the MtrC, confirming that electrons are transferred from the TiO₂ nanocrystals to the surface via the MtrC conduit. In other words, in these TiO₂/MtrC hybrid photodiodes, MtrC traps the conduction-band electrons from TiO₂ before transferring them to the electrode, creating a photobioelectrochemical system in which a redox protein is used to mimic the efficient charge separation found in biological photosystems.

The photocatalytic activity of phosphonated Re complexes, [Re(2,2′-bipyridine-4,4′-bisphosphonic acid) (CO)₃(L)] (ReP; L=3-picoline or bromide) immobilised on TiO₂ nanoparticles is reported. The heterogenised Re catalyst on the semiconductor, ReP–TiO₂ hybrid, displays an improvement in CO₂ reduction photocatalysis. A high turnover number (TON) of 48 mol_CO mol_Re⁻¹ is observed in DMF with the electron donor triethanolamine at λ>420 nm. ReP–TiO₂ compares favourably to previously reported homogeneous systems and is the highest TON reported to date for a CO₂-reducing Re photocatalyst under visible light irradiation. Photocatalytic CO₂ reduction is even observed with ReP–TiO₂ at wavelengths of λ>495 nm. Infrared and X-ray photoelectron spectroscopies confirm that an intact ReP catalyst is present on the TiO₂ surface before and during catalysis. Transient absorption spectroscopy suggests that the high activity upon heterogenisation is due to an increase in the lifetime of the immobilised anionic Re intermediate (t_50 %>1 s for ReP–TiO₂ compared with t_50 %=60 ms for ReP in solution) and immobilisation might also reduce the formation of inactive Re dimers. This study demonstrates that the activity of a homogeneous photocatalyst can be improved through immobilisation on a metal oxide surface by favourably modifying its photochemical kinetics.

An efficient, stable and scalable hybrid photoelectrode for visible-light-driven H₂ generation in an aqueous pH 9.2 electrolyte solution is reported. The photocathode consists of a p-type Si substrate layered with a Ti and Ni-containing composite film, which acts as both a protection and electrocatalyst layer on the Si substrate. The film is prepared by the simple drop casting of the molecular single-source precursor, [{Ti₂(OEt)₉(NiCl)}₂] (TiNi_pre), onto the p-Si surface at room temperature, followed by cathodic in situ activation to form the catalytically active TiNi film (TiNi_cat). The p-Si|TiNi_cat photocathode exhibits prolonged hydrogen generation with a stable photocurrent of approximately −5 mA cm⁻² at 0 V vs. RHE in an aqueous pH 9.2 borate solution for several hours, and serves as a benchmark non-noble photocathode for solar H₂ evolution that operates efficiently under neutral–alkaline conditions.

Formic acid is considered a promising energy carrier and hydrogen storage material for a carbon-neutral economy. We present an inexpensive system for the selective room-temperature photocatalytic conversion of formic acid into either hydrogen or carbon monoxide. Under visible-light irradiation (λ>420 nm, 1 sun), suspensions of ligand-capped cadmium sulfide nanocrystals in formic acid/sodium formate release up to 116±14 mmol H₂ g_cat⁻¹ h⁻¹ with >99 % selectivity when combined with a cobalt co-catalyst; the quantum yield at λ=460 nm was 21.2±2.7 %. In the absence of capping ligands, suspensions of the same photocatalyst in aqueous sodium formate generate up to 102±13 mmol CO g_cat⁻¹ h⁻¹ with >95 % selectivity and 19.7±2.7 % quantum yield. H₂ and CO production was sustained for more than one week with turnover numbers greater than 6×10⁵ and 3×10⁶, respectively.

Formic acid is considered a promising energy carrier and hydrogen storage material for a carbon-neutral economy. We present an inexpensive system for the selective room-temperature photocatalytic conversion of formic acid into either hydrogen or carbon monoxide. Under visible-light irradiation (λ>420 nm, 1 sun), suspensions of ligand-capped cadmium sulfide nanocrystals in formic acid/sodium formate release up to 116±14 mmol H₂ g_cat⁻¹ h⁻¹ with >99 % selectivity when combined with a cobalt co-catalyst; the quantum yield at λ=460 nm was 21.2±2.7 %. In the absence of capping ligands, suspensions of the same photocatalyst in aqueous sodium formate generate up to 102±13 mmol CO g_cat⁻¹ h⁻¹ with >95 % selectivity and 19.7±2.7 % quantum yield. H₂ and CO production was sustained for more than one week with turnover numbers greater than 6×10⁵ and 3×10⁶, respectively.

A dinuclear synthetic model of the [NiFeSe] hydrogenase active site and a structural, spectroscopic and electrochemical analysis of this complex is reported. [NiFe(‘S₂Se₂’)(CO)₃] (H₂‘S₂Se₂’=1,2-bis(2-thiabutyl-3,3-dimethyl-4-selenol)benzene) has been synthesized by reacting the nickel selenolate complex [Ni(‘S₂Se₂’)] with [Fe(CO)₃bda] (bda=benzylideneacetone). X-ray crystal structure analysis confirms that [NiFe(‘S₂Se₂’)(CO)₃] mimics the key structural features of the enzyme active site, including a doubly bridged heterobimetallic nickel and iron center with a selenolate terminally coordinated to the nickel center. Comparison of [NiFe(‘S₂Se₂’)(CO)₃] with the previously reported thiolate analogue [NiFe(‘S₄’)(CO)₃] (H₂‘S₄’=H₂xbsms=1,2-bis(4-mercapto-3,3-dimethyl-2-thiabutyl)benzene) showed that the selenolate groups in [NiFe(‘S₂Se₂’)(CO)₃] give lower carbonyl stretching frequencies in the IR spectrum. Electrochemical studies of [NiFe(‘S₂Se₂’)(CO)₃] and [NiFe(‘S₄’)(CO)₃] demonstrated that both complexes do not operate as homogenous H₂ evolution catalysts, but are precursors to a solid deposit on an electrode surface for H₂ evolution catalysis in organic and aqueous solution.

Solar-light-driven H₂ production in water with a [NiFeSe]-hydrogenase (H₂ase) and a bioinspired synthetic nickel catalyst (NiP) in combination with a heptazine carbon nitride polymer, melon (CN_x), is reported. The semibiological and purely synthetic systems show catalytic activity during solar light irradiation with turnover numbers (TONs) of more than 50 000 mol H₂ (mol H₂ase)⁻¹ and approximately 155 mol H₂ (mol NiP)⁻¹ in redox-mediator-free aqueous solution at pH 6 and 4.5, respectively. Both systems maintained a reduced photoactivity under UV-free solar light irradiation (λ>420 nm).

Solar-light-driven H₂ production in water with a [NiFeSe]-hydrogenase (H₂ase) and a bioinspired synthetic nickel catalyst (NiP) in combination with a heptazine carbon nitride polymer, melon (CN_x), is reported. The semibiological and purely synthetic systems show catalytic activity during solar light irradiation with turnover numbers (TONs) of more than 50 000 mol H₂ (mol H₂ase)⁻¹ and approximately 155 mol H₂ (mol NiP)⁻¹ in redox-mediator-free aqueous solution at pH 6 and 4.5, respectively. Both systems maintained a reduced photoactivity under UV-free solar light irradiation (λ>420 nm).

A visible-light driven H₂ evolution system comprising of a Ru^II dye (RuP) and Co^III proton reduction catalysts (CoP) immobilised on TiO₂ nanoparticles and mesoporous films is presented. The heterogeneous system evolves H₂ efficiently during visible-light irradiation in a pH-neutral aqueous solution at 25 °C in the presence of a hole scavenger. Photodegradation of the self-assembled system occurs at the ligand framework of CoP, which can be readily repaired by addition of fresh ligand, resulting in turnover numbers above 300 mol H₂ (mol CoP)⁻¹ and above 200,000 mol H₂ (mol TiO₂ nanoparticles)⁻¹ in water. Our studies support that a molecular Co species, rather than metallic Co or a Co-oxide precipitate, is responsible for H₂ formation on TiO₂. Electron transfer in this system was studied by transient absorption spectroscopy and time-correlated single photon counting techniques. Essentially quantitative electron injection takes place from RuP into TiO₂ in approximately 180 ps. Thereby, upon dye regeneration by the sacrificial electron donor, a long-lived TiO₂ conduction band electron is formed with a half-lifetime of approximately 0.8 s. Electron transfer from the TiO₂ conduction band to the CoP catalysts occurs quantitatively on a 10 μs timescale and is about a hundred times faster than charge-recombination with the oxidised RuP. This study provides a benchmark for future investigations in photocatalytic fuel generation with molecular catalysts integrated in semiconductors.