Solar‐to‐Hydrogen Energy Conversion Based on Water Splitting

Artificial photosynthesis provides a blueprint to harvest solar energy to sustain the future energy demands. Solar‐driven water splitting, converting solar energy into hydrogen energy, is the prototype of photosynthesis. Various systems have been designed and evaluated to understand the reaction pathways and/or to meet the requirements of potential applications. In solar‐to‐hydrogen conversion, electrocatalytic hydrogen and oxygen evolution reactions are key research areas that are meaningful both theoretically and practically. To utilize hydrogen energy, fuel cell technology has been extensively investigated because of its high efficiency in releasing chemical energy. In this review, general concepts of the photosynthesis in green plants are discussed, different strategies for the light‐driven water splitting proposed in laboratories are introduced, the progress of electrocatalytic hydrogen and oxygen evolution reactions are reviewed, and finally, the reactions in hydrogen fuel cells are briefly discussed. Overall, the mass and energy circulation in the solar‐hydrogen‐electricity circle are delineated. The authors conclude that attention from scientists and engineers of relevant research areas is still highly needed to eliminate the wide disparity between the aspirations and realities of artificial photosynthesis.     

Boosting Oxygen Evolution Kinetics by Mn–N–C Motifs with Tunable Spin State for Highly Efficient Solar‐Driven Water Splitting

Solar‐driven water splitting is in urgent need for sustainable energy research, for which accelerating oxygen evolution kinetics along with charge migration is the key issue. Herein, Mn³⁺ within π‐conjugated carbon nitride (C₃N₄) in form of Mn–N–C motifs is coordinated. The spin state (e_g orbital filling) of Mn centers is regulated by controlling the bond strength of Mn–N. It is demonstrated that Mn serves as intrinsic oxygen evolution reaction (OER) site and the kinetics is dependent on its spin state with an optimized e_g occupancy of ≈0.95. Specifically, the governing role of e_g occupancy originates from the varied binding strength between Mn and OER intermediates. Benefiting from the rapid spin state‐mediated OER kinetics, as well as extended optical absorption (to 600 nm) and accelerated charge separation by intercalated metal‐to‐ligand state, Mn–C₃N₄ stoichiometrically splits pure water with H₂ production rate up to 695.1 µmol g^?1 h^?1 under simulated sunlight irradiation (AM1.5), and achieves an apparent quantum efficiency of 4.0% at 420 nm, superior to most solid‐state based photocatalysts to date. This work for the first time correlates photocatalytic redox kinetics with the spin state of active sites, and suggests a nexus between photocatalysis and spin theory.     

Modifying La0.6Sr0.4MnO3 Perovskites with Cr Incorporation for Fast Isothermal CO2‐Splitting Kinetics in Solar‐Driven Thermochemical Cycles

Perovskites are promising oxygen carriers for solar‐driven thermochemical fuel production due to higher oxygen exchange capacity. Despite their higher fuel yield capacity, La_0.6Sr_0.4MnO₃ perovskite materials present slow CO₂‐splitting kinetics compared with state‐of‐the‐art CeO₂. In order to improve the CO production rates, the incorporation of Cr in La_0.6Sr_0.4MnO₃ is explored based on thermodynamic calculations that suggest an enhanced driving force toward CO₂ splitting at high temperatures for La_0.6Sr_0.4Cr_xMn_1?xO₃ perovskites. Here, reported is a threefold faster CO fuel production for La_0.6Sr_0.4Cr_0.85Mn_0.15O₃ compared to conventional La_0.6Sr_0.4MnO₃, and twofold faster than CeO₂ under isothermal redox cycling at 1400 °C, and high stability upon long‐term cycling without any evidence of microstructural degradation. The findings suggest that with the proper design in terms of transition metal ion doping, it is possible to adjust perovskite compositions and reactor conditions for improved solar‐to‐fuel thermochemical production under nonconventional solar‐driven thermochemical cycling schemes such as the here presented near isothermal operation.     

Solar‐Light‐Driven CO2 Reduction by CH4 on Silica‐Cluster‐Modified Ni Nanocrystals with a High Solar‐to‐Fuel Efficiency and Excellent Durability

Catalytic CO₂ reforming of CH₄ (CRM) to produce syngas (H₂ and CO) provides a promising approach to reducing global CO₂ emissions and the extensive utilization of natural gas resources. However, the rapid deactivation of the reported catalysts due to severe carbon deposition at high reaction temperatures and the large energy consumption of the process hinder its industrial application. Here, a method for almost completely preventing carbon deposition is reported by modifying the surface of Ni nanocrystals with silica clusters. The obtained catalyst exhibits excellent durability for CRM with almost no carbon deposition and deactivation after reaction for 700 h. Very importantly, it is found that CRM on the catalyst can be driven by focused solar light, thus providing a promising new approach to the conversion of renewable solar energy to fuel due to the highly endothermic characteristics of CRM. The reaction yields high production rates of H₂ and CO (17.1 and 19.9 mmol min^?1 g^?1, respectively) with a very high solar‐to‐fuel efficiency (η, 12.5%). Even under focused IR irradiation with a wavelength above 830 nm, the η of the catalyst remains as high as 3.1%. The highly efficient catalytic activity arises from the efficient solar‐light‐driven thermocatalytic CRM enhanced by a novel photoactivation effect.     

Self‐Contained Monolithic Carbon Sponges for Solar‐Driven Interfacial Water Evaporation Distillation and Electricity Generation

Solar vaporization has received tremendous attention for its potential in desalination, sterilization, distillation, etc. However, a few major roadblocks toward practical application are the high cost, process intensive, fragility of solar absorber materials, and low efficiency. Herein an inexpensive cellular carbon sponge that has a broadband light absorption and inbuilt structural features to perform solitary heat localization for in situ photothermic vaporization is reported. The defining advantages of elastic cellular porous sponge are that it self‐confines water to the perpetually hot spots and accommodates cyclical dynamic fluid flow‐volume variable stress for practical usage. By isolating from bulk water, the solar‐to‐vapor conversion efficiency is increased by 2.5‐fold, surpassing that of conventional bulk heating. Notably, complementary solar steam generation‐induced electricity can be harvested during the solar vaporization so as to capitalize on waste heat. Such solar distillation and waste heat‐to‐electricity generation functions may provide potential opportunities for on‐site electricity and fresh water production for remote areas/emergency needs.     

Considerations in the Design of Materials for Solar‐Driven Fuel Production Using Metal‐Oxide Thermochemical Cycles

With demand for energy increasing worldwide and an ever‐stronger case building for anthropogenic climate change, the need for carbon‐neutral fuels is becoming an imperative. Extensive transportation infrastructure based on liquid hydrocarbon fuels motivates development of processes using solar energy to convert CO₂ and H₂O to fuel precursors such as synthesis gas. Here, perspectives concerning the use of solar‐driven thermochemical cycles using metal oxides to produce fuel precursors are given and, in particular, the important relationship between reactor design and material selection is discussed. Considering both a detailed thermodynamic analysis and factors such as reaction kinetics, volatility, and phase stability, an integrated analytical approach that facilitates material design is presented. These concepts are illustrated using three oxide materials currently receiving considerable attention: metal‐substituted ferrites, ceria, and doped cerias. Although none of these materials is “ideal,” the tradeoffs made in selecting any one of them are clearly indicated, providing a starting point for assessing the feasibility of alternative materials developed in the future.     

Highly Efficient Solar‐Driven Carbon Dioxide Reduction on Molybdenum Disulfide Catalyst Using Choline Chloride‐Based Electrolyte

Conversion of CO₂ to energy‐rich chemicals using renewable energy is of much interest to close the anthropogenic carbon cycle. However, the current photoelectrochemical systems are still far from being practically feasible. Here the successful demonstration of a continuous, energy efficient, and scalable solar‐driven CO₂ reduction process based on earth‐abundant molybdenum disulfide (MoS₂) catalyst, which works in synergy with an inexpensive hybrid electrolyte of choline chloride (a common food additive for livestock) and potassium hydroxide (KOH) is reported. The CO₂ saturated hybrid electrolyte utilized in this study also acts as a buffer solution (pH ≈ 7.6) to adjust pH during the reactions. This study reveals that this system can efficiently convert CO₂ to CO with solar‐to‐fuel and catalytic conversion efficiencies of 23% and 83%, respectively. Using density functional theory calculations, a new reaction mechanism in which the water molecules near the MoS₂ cathode act as proton donors to facilitate the CO₂ reduction process by MoS₂ catalyst is proposed. This demonstration of a continuous, cost‐effective, and energy efficient solar driven CO₂ conversion process is a key step toward the industrialization of this technology.     

Continuous 3D Titanium Nitride Nanoshell Structure for Solar‐Driven Unbiased Biocatalytic CO2 Reduction

Z‐scheme‐inspired tandem photoelectrochemical (PEC) cells have received attention as a sustainable platform for solar‐driven CO₂ reduction. Here, continuously 3D‐structured, electrically conductive titanium nitride nanoshells (3D TiN) for biocatalytic CO₂‐to‐formate conversion in a bias‐free tandem PEC system are reported. The 3D TiN exhibits a periodically porous network with high porosity (92.1%) and conductivity (6.72 × 10⁴ S m^?1), which allows for high enzyme loading and direct electron transfer (DET) to the immobilized enzyme. It is found that the W‐containing formate dehydrogenase from Clostridium ljungdahlii (ClFDH) on the 3D TiN nanoshell is electrically activated through DET for CO₂ reduction. At a low overpotential of 40 mV, the 3D TiN‐ClFDH stably converts CO₂ to formate at a rate of 0.34 µmol h^?1 cm^?2 and a faradaic efficiency (FE) of 93.5%. Compared to a flat TiN‐ClFDH, the 3D TiN‐ClFDH shows a 58 times higher formate production rate (1.74 µmol h^?1 cm^?2) at 240 mV of overpotential. Lastly, a bias‐free biocatalytic tandem PEC cell that converted CO₂ to formate at an average rate of 0.78 µmol h^?1 and an FE of 77.3% only using solar energy and water is successfully assembled.     

Efficient Solar‐Driven Water Oxidation over Perovskite‐Type BaNbO2N Photoanodes Absorbing Visible Light up to 740 nm

Photoelectrochemical water splitting using semiconductors absorbing a wide range of visible light is a potentially attractive means of harvesting large portions of the solar spectrum. However, this is also very challenging because narrowing the semiconductor band gap lowers the driving force for photoreactions. Herein, a highly active perovskite BaNbO₂N exhibiting photoexcitation up to 740 nm for water oxidation is reported. The synthesis route, consisting of moderate nitridation and subsequent annealing in inert Ar flow, enhances the crystallinity of the BaNbO₂N surface without inducing the reduction of the Nb species. As a result, a particulate BaNbO₂N photoanode exhibits a photocurrent of 5.2 mA cm^?2 at 1.23 V_RHE under simulated solar irradiation, which is the highest yet reported for an oxynitride responsive at wavelengths above 600 nm. Suppressing the reduction of B‐site cations during the synthesis of perovskite AB(O,N)₃, which otherwise results in surface defects or impurities, is critical for achieving high water oxidation activity.     

Interfacial Solar‐to‐Heat Conversion for Desalination

Solar desalination is a promising and sustainable solution for water shortages in the future. Interfacial solar‐to‐heat conversion for desalination has attracted increasing attention in the past decades, due to the heat localization induced high thermal efficiency, simple structure, and low cost. In this review, the authors summarize and analyze the critical processes involved in such a solar desalination system, including the thermal conversion and transport, salt dissipation, and vapor manipulation. Mathematical models of heat transfer and salt dissipation are also built for quantitative analysis of systematic performance relative to properties of employed materials and system designs. Recent efforts devoted to improving the overall thermal efficiency, salt rejection, and water yield are then summarized. Based on the analysis and previous results, opportunities for further interfacial solar desalination development are highlighted.     

Light‐Induced Activation of Adaptive Junction for Efficient Solar‐Driven Oxygen Evolution: In Situ Unraveling the Interfacial Metal–Silicon Junction

The integration of surface metal catalysts with semiconductor absorbers to produce photocatalytic devices is an attractive method for achieving high‐efficiency solar‐induced water splitting. However, once combined with a photoanode, detailed discussions of the light‐induced processes on metal/semiconductor junction remain largely inadequate. Here, by employing in situ X‐ray scattering/diffraction and absorption spectroscopy, the generation of a photoinduced adaptive structure is discovered at the interfacial metal–semiconductor (M–S) junction between a state‐of‐the‐art porous silicon wire and nickel electrocatalyst, where oxygen evolution occurs under illumination. The adaptive layer in M–S junction through the light‐induced activation can enhance the voltage by 247 mV (to reach a photocurrent density of 10 mA cm^?2) with regard to the fresh photoanode, and increase the photocurrent density by six times at the potential of 1.23 V versus reversible reference electrode (RHE). This photoinduced adaptive layer offers a new perspective regarding the catalytic behavior of catalysts, especially for the photocatalytic water splitting of the system, and acting as a key aspect in the development of highly efficient photoelectrodes.     

Metal Halide Perovskites for Solar‐to‐Chemical Fuel Conversion

This review article presents and discusses the recent progress made in the stabilization, protection, improvement, and design of halide perovskite‐based photocatalysts, photoelectrodes, and devices for solar‐to‐chemical fuel conversion. With the target of water splitting, hydrogen iodide splitting, and CO₂ reduction reactions, the strategies established for halide perovskites used in photocatalytic particle‐suspension systems, photoelectrode thin‐film systems, and photovoltaic‐(photo)electrocatalysis tandem systems are organized and introduced. Moreover, recent achievements in discovering new and stable halide perovskite materials, developing protective and functional shells and layers, designing proper reaction solution systems, and tandem device configurations are emphasized and discussed. Perspectives on the future design of halide perovskite materials and devices for solar‐to‐chemical fuel conversion are provided. This review may serve as a guide for researchers interested in utilizing halide perovskite materials for solar‐to‐chemical fuel conversion.