Shape Conformal and Thermal Insulative Organic Solar Absorber Sponge for Photothermal Water Evaporation and Thermoelectric Power Generation

Solar‐driven interfacial vaporization by localizing solar‐thermal energy conversion to the air–water interface has attracted tremendous attention due to its high conversion efficiency for water purification, desalination, energy generation, etc. However, ineffective integration of hybrid solar thermal devices and poor material compliance undermine extensive solar energy exploitation and practical outdoor use. Herein, a 3D organic bucky sponge that has a combination of desired chemical and physical properties, i.e., broadband light absorbing, heat insulative, and shape‐conforming abilities that render efficient photothermic vaporization and energy generation with improved operational durability is reported. The highly compressible and readily reconfigurable solar absorber sponge not only places less constraints on footprint and shape defined fabrication process but more importantly remarkably improves the solar‐to‐vapor conversion efficiency. Notably, synergetic coupling of solar‐steam and solar‐electricity technologies is realized without trade‐offs, highlighting the practical consideration toward more impactful solar heat exploitation. Such solar distillation and low‐grade heat‐to‐electricity generation functions can provide potential opportunities for fresh water and electricity supply in off‐grid or remote areas.     

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.     

Superwetting Monolithic Hollow‐Carbon‐Nanotubes Aerogels with Hierarchically Nanoporous Structure for Efficient Solar Steam Generation

Solar steam generation has been proven to be one of the most efficient approaches for harvesting solar energy for diverse applications such as distillation, desalination, and production of freshwater. Here, the synthesis of monolithic carbon aerogels by facile carbonization of conjugated microporous polymer nanotubes as efficient solar steam generators is reported. The monolithic carbon‐aerogel networks consist of randomly aggregated hollow‐carbon‐nanotubes (HCNTs) with 100–250 nm in diameter and a length of up to several micrometers to form a hierarchically nanoporous network structure. Treatment of the HCNTs aerogels with an ammonium peroxydisulfate/sulfuric acid solution endows their superhydrophilic wettability which is beneficial for rapid transportation of water molecules. In combination with their abundant porosity (92%) with open channel structure, low apparent density (57 mg cm^?3), high specific surface area (826 m² g^?1), low thermal conductivity (0.192 W m^?1 K^?1), and broad light absorption (99%), an exceptionally high conversion efficiency of 86.8% is achieved under 1 sun irradiation, showing great potential as an efficient photothermal material for solar steam generation. The findings may provide a new opportunity for tailored design and creation of new carbon‐aerogels‐based photothermal materials with adjustable structure, tunable porosity, simple fabrication process, and high solar energy conversion efficiency for solar steam generation.     

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.     

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.     

Synthesis of Black TiOx Nanoparticles by Mg Reduction of TiO2 Nanocrystals and their Application for Solar Water Evaporation

TiO_x (x < 2) nanoparticles with tunable colors from white to gray to blue–gray to black are synthesized by magnesium (Mg) reduction of white P25 TiO₂ nanocrystals followed by removal of excess Mg with aqueous HCl and distilled water. Increasing amounts of Mg smoothly decrease the oxygen content in TiO_x which is responsible for the gradual increase in light absorption and concomitant darkening of its color from white to black with decreasing values of x. The as‐synthesized TiO_x nanoparticles are spin‐coated onto the surface of a stainless steel mesh followed by surface superhydrophobization in order to test their performance as a solar water evaporator. Results from the tests show that the black TiO_x efficiently generates water vapor with a solar thermal conversion efficiency as high as 50% under solar‐simulated light irradiance at an intensity of 1000 W m^–2 (1 Sun). Moreover, TiO_x nanoparticles have inherent advantages over other materials used for solar water desalination, such as their tunable light absorption, low‐cost, low‐toxicity, superhydrophobicity, and chemical stability.     

Superb Alkaline Hydrogen Evolution and Simultaneous Electricity Generation by Pt‐Decorated Ni3N Nanosheets

The development of efficient hydrogen evolution reaction electrocatalysts is critical to the realization of clean hydrogen fuel production, while the sluggish kinetics of the Volmer‐step substantially restricts the catalyst performances in alkali electrolyzers, even for noble metal catalysts such as Pt. Here, a Pt‐decorated Ni₃N nanosheet electrocatalyst is developed to achieve a top performance of hydrogen evolution in alkaline conditions. Possessing a high metallic conductivity and an atomic‐thin semiconducting hydroxide surface, the Ni₃N nanosheets serve as not only an efficient electron pathway without the hindrance of Schottky barriers, but also provide abundant active sites for water dissociation and generation of hydrogen intermediates, which are further adsorbed on the Pt surface to recombine to H₂. The Pt‐decorated Ni₃N nanosheet catalyst exhibits a hydrogen evolution current density of 200 mA cm^?2 at an overpotential of 160 mV versus reversible hydrogen electrode, a Tafel slope of ≈36.5 mV dec^?1, and excellent stability of 82.5% current retention after 24 h of operation. Moreover, a hybrid cell consisting of a Pt‐decorated Ni₃N nanosheet cathode and a Li‐metal anode is assembled to achieve simultaneous hydrogen evolution and electricity generation, exhibiting >60 h long‐term hydrogen evolution reaction stability and an output voltage ranging from 1.3 to 2.2 V.     

Boron Nanoparticles for Room‐Temperature Hydrogen Generation from Water

Boron nanoparticles (BNPs) are of great interest for applications such as neutron capture therapy of cancer cells, hydrogen generation from water, and high energy density fuels. Boron is particularly interesting for chemical water splitting, because of its high gravimetric hydrogen generation potential of 277 g H₂ per kg B. However, only a few studies of water splitting by reaction with boron are available, and those have used high temperature steam with external heating. Room‐temperature boron hydrolysis is of great interest from both scientific and practical perspectives. The studies presented here demonstrate that high purity amorphous BNPs can be oxidized by water to produce H₂ at room temperature, without external energy input, in the presence of catalytic quantities of an alkali metal or alkali metal hydride. The BNPs are produced in a single step gas phase process via CO₂ laser‐induced pyrolysis of mixtures of B₂H₆ and SF₆. The BNPs are spherical with a primary particle diameter of 10–15 nm, narrow size distribution, and specific surface area exceeding 250 m² g^?1. This first demonstration of room‐temperature chemical splitting of liquid water using boron opens up exciting new possibilities for on‐demand hydrogen generation at high gravimetric capacity.     

Polydopamine‐Inspired,Dual Heteroatom‐Doped Carbon Nanotubes for Highly Efficient Overall Water Splitting

Overall water splitting involved hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are critical for renewable energy conversion and storage. Heteroatom‐doped carbon materials have been extensively employed as efficient electrocatalysts for independent HER or OER processes, while those as the bifunctional catalysts for simultaneously generating H₂ and O₂ by splitting water have been seldom reported. Inspired by the unparalleled virtues of polydopamine, the authors devise the facile synthesis of nitrogen and sulfur dual‐doped carbon nanotubes with in situ, homogenous and high concentration sulfur doping. The newly developed dual‐doped electrocatalysts display superb bifunctional catalytic activities for both HER and OER in alkaline solutions, outperforming all other reported carbon counterparts. Experimental characterizations confirm that the excellent performance is attributed to the multiple doping together with efficient mass and charge transfer, while theoretical computations reveal the promotion effect of secondary sulfur dopant to enhance the spin density of dual‐doped samples and consequently to form highly electroactive sites for both HER and OER.