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.     

Pore Structure Controlling the Activity of Mesoporous Crystalline CsTaWO6 for Photocatalytic Hydrogen Generation

The quaternary oxide CsTaWO₆ exhibits a very high activity for photocatalytic hydrogen generation and water splitting. To improve its properties with regard to photocatalytic applications, it is prepared with mesoporous morphology for the first time, utilizing a template‐based evaporation‐induced self‐assembly process. The resulting material exhibits a median mesopore size of 10 nm, a surface area of 60 m² g^?1, and high crystallinity after preparation at 550 °C with phase‐pure defect‐pyrochlore structure. To further improve the textural properties of mesoporous CsTaWO₆, the addition of additives to the synthesis procedure is also investigated. By using H₂SO₄/HCl and a carbonization/oxidation procedure, the surface area of the resulting mesoporous CsTaWO₆ is increased to 78 m² g^?1, which is a 20‐fold increase compared to a nonporous reference via sol‐gel preparation, also leading to improved photocatalytic activity. By investigating the ability for photocatalytic hydrogen generation, the importance of high surface area and pore diameter of the resulting materials in comparison to nonporous materials is presented. Interestingly, the photocatalytic activity does not increase linearly with surface area, due to a strong influence of the pore diameter on the photocatalytic activity.     

Architecting Nitrogen Functionalities on Graphene Oxide Photocatalysts for Boosting Hydrogen Production in Water Decomposition Process

This study elucidates how nitrogen functionalities influence the transition and transfer of photogenerated electrons in graphene‐based materials. Graphene oxide dots (GODs) and Nitrogen‐doped GODs (NGODs) are synthesized by thermally treating graphene oxide (GO) sheets in argon and ammonia, respectively, and then ultrasonically exfoliating the sheets in nitric acid. The nitrogen functionalities of NGODs are mainly quaternary/pyridinic/pyrrolic, and the nitrogen atoms in these functionalities are planar to the GO sheets and repair the vacancy defects on the sheets. Hydrothermal treatment of NGODs in ammonia yields ammonia‐treated NGODs (A‐NGODs), with some pyridinic/pyrrolic groups being converted to amino/amide groups. The nitrogen atoms in the amino/amide groups are not planar to the GO sheets and are prone to donate their lone pair electrons to resonantly conjugate with the aromatic π electrons. The promoted conjugation facilitates the relaxation of photogenerated electrons to the triplet states and prolongs the electron lifetime. When deposited with Pt as the co‐catalyst, the samples catalyze H₂ production from an aqueous triethanolamine solution under 420 nm monochromatic irradiation at quantum yields of 7.3% (GODs), 9.7% (NGODs), and 21% (A‐NGODs). The high activity of A‐NGODs demonstrates that architecting nitrogen functionalities effectively mediate charge motion in carbon‐based materials for application to photoenergy conversion.     

Photocatalytic Water Splitting for Solar Hydrogen Production Using the Carbonate Effect and the Z‐Scheme Reaction

The development of innovative technologies for solar energy conversion and storage is important for solving the global warming problem and for establishing a sustainable society. The photocatalytic water‐splitting reaction using semiconductor powders has been intensively studied as a promising technology for direct and simple solar energy conversion. However, the evolution of H₂ and O₂ gases in a stoichiometric ratio (H₂/O₂ = 2) is very difficult owing to various issues, such as an unfavorable backward reaction and mismatched band potentials. Two important findings have widened the variety of photocatalysts available for stoichiometric water‐splitting, viz. the carbonate anion effect and the Z‐scheme photocatalytic reaction using a redox mediator. The bicarbonate anion has been found to act as a redox catalyst via preferential peroxide formation and subsequent decomposition to O₂. As the Z‐scheme reaction using a redox mediator mitigates band potential mismatches, it is widely applicable for various visible‐light‐active photocatalysts. This review describes the development of photocatalytic water‐splitting for solar hydrogen production using the carbonate anion effect and the Z‐scheme reaction. Moreover, recent developments in photocatalysis–electrolysis hybrid systems, an advanced Z‐scheme reaction concept, are also reviewed for practical and economical hydrogen production.     

Transition Metal Disulfides as Noble‐Metal‐Alternative Co‐Catalysts for Solar Hydrogen Production

The production of hydrogen fuels by using sunlight is an attractive and sustainable solution to the global energy and environmental problems. Platinum (Pt) is known as the most efficient co‐catalyst in hydrogen evolution reaction (HER). However, due to its high‐cost and limited‐reserves, it is highly demanded to explore alternative non‐precious metal co‐catalysts with low‐cost and high efficiency. Transition metal disulfides (TMDs) including molybdenum disulfide and tungsten disulfide have been regarded as promising candidates to replace Pt for HER in recent years. Their unique structural and electronic properties allow them to have many opportunities to be designed as highly efficient co‐catalysts over various photo harvesting semiconductors. Recent progress in TMDs as photo‐cocatalysts in solar hydrogen production field is summarized, focusing on the effect of structural matchability with photoharvesters, band edges tunability, and phase transformation on the improvement of hydrogen production activities. Moreover, recent research efforts toward the TMDs as more energy‐efficient and economical co‐catalysts for HER are highlighted. Finally, this review concludes by critically summarizing both findings and current perspectives, and highlighting crucial issues that should be addressed in future research activities.     

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.     

Biomimetic MXene Textures with Enhanced Light‐to‐Heat Conversion for Solar Steam Generation and Wearable Thermal Management

2D materials are of particular interest in light‐to‐heat conversion, yet challenges remain in developing a facile method to suppress their light reflection. Herein, inspired by the black scales of Bitis rhinoceros, a generalized approach via sequential thermal actuations to construct biomimetic 2D‐material nanocoatings, including Ti₃C₂T_x MXene, reduced graphene oxide (rGO), and molybdenum disulfide (MoS₂) is designed. The hierarchical MXene nanocoatings result in broadband light absorption (up to 93.2%), theoretically validated by optical modeling and simulations, and realize improved light‐to‐heat performance (equilibrium temperature of 65.4 °C under one‐sun illumination). With efficient light‐to‐heat conversion, the bioinspired MXene nanocoatings are next incorporated into solar steam‐generation devices and stretchable solar/electric dual‐heaters. The MXene steam‐generation devices require much lower solar‐thermal material loading (0.32 mg cm^?2) and still guarantee high steam‐generation performance (1.33 kg m^?2 h^?1) compared with other state‐of‐the‐art devices. Additionally, the mechanically deformed MXene structures enable the fabrication of stretchable and wearable heaters dual‐powered by sunlight and electricity, which are reversibly stretched and heated above 100 °C. This simple fabrication process with effective utilization of active materials promises its practical application value for multiple solar–thermal technologies.     

污泥与餐厨垃圾发酵产氢种泥预处理方法比较

以剩余污泥和餐厨垃圾作为混合基质进行厌氧发酵产氢批式试验,比较六种常用的产氢种泥预处理方法[热处理、化学抑制剂2-溴乙基磺酸钠(BESA)处理、酸处理、碱处理、连续曝气、重复曝气]对产氢的影响。结果表明,未经预处理的种泥氢气产率最低,且有明显的吸氢和产甲烷现象。BESA处理、酸处理、连续曝气和重复曝气种泥产氢效果较好,其中重复曝气预处理种泥氢气产率最高,为86.9 ml-H2/g-VSadded,对产甲烷菌有明显抑制。热处理和碱处理种泥产氢效果较差,反应后期出现吸氢反应并有明显的甲烷累积现象。发酵产氢过程中p H值从中性下降到5.0左右,对产甲烷菌活性也具有一定的抑制作用。     

Benchmarking the Activity,Stability, and Inherent Electrochemistry of Amorphous Molybdenum Sulfide for Hydrogen Production

Anodically electrodeposited amorphous molybdenum sulfide (AE‐MoS_x) has attracted significant attention as a non‐noble metal electrocatalyst for its high activity toward the hydrogen evolution reaction (HER). The [Mo₃S₁₃]^2? polymer‐based structure confers a high density of exposed sulfur moieties, widely regarded as the HER active sites. However, their intrinsic complexity conceals full understanding of their exact role in HER catalysis, hampering their full potential for water splitting applications. In this report, a unifying approach is adopted accounting for modifications in the inherent electrochemistry (EC), HER mechanism, and surface species to maximize the AE‐MoS_x electroactivity over a broad pH region (0–10). Dramatic enhancements in HER performance by selective electrochemical cycling within reductive (overpotential shift, η_HER ≈ ?350 mV) and electro‐oxidative windows (η_HER ≈ ?290 mV) are accompanied by highly stable performance in mildly acidic electrolytes. Joint analysis of X‐ray photoelectron spectroscopy, Raman, and EC experiments corroborate the key role of bridging and terminal S ligands as active site generators at low pH, and reveal molybdenum oxysulfides (Mo⁵⁺O_xS_y) to be the most active HER moiety in AE‐MoS_x in mildly acidic‐to‐neutral environments. These findings will be extremely beneficial for future tailoring of MoS_x materials and their implementation in commercial electrolyzer technologies.     

UV‐Rearranged PIM‐1 Polymeric Membranes for Advanced Hydrogen Purification and Production

Polymers of intrinsic microporosity (PIM‐1) have been known for their super high permeability but average selectivity for medium‐size gas pairs. They have unimpressive selectivity for H₂ and CO₂ separation (i.e., α (H₂/CO₂) = 0.6). For the first time, we have discovered that ultraviolet (UV)‐rearranged polymers of PIM‐1 membranes can be used for H₂/CO₂ separation with far superior separation performance to others in literatures. The PIM‐1 membrane after UV radiation for 4 hours shows H₂ permeability of 452 barrer with H₂/CO₂ selectivity of 7.3. Experimental data and molecular simulation reveal that the polymer chains of PIM‐1 undergo 1,2‐migration reaction and transform to close‐to‐planar like rearranged structure after UV radiation. As a result, the UV‐irradiated PIM‐1 membrane shows considerable drops in both fractional free volume (FFV) and size of micro‐pores. Positron annihilation lifetime (PAL) results have confirmed the chemical and structural changes, suggesting the FFV and pore size drops are mainly ascribed to the destructed spiro‐carbon centre during UV radiation. Sorption and x‐ray diffractor (XRD) analyses indicate that the impressive H₂/CO₂ selectivity arises from the significantly enhanced diffusivity selectivity induced by UV radiation, followed by molecular rearrangement, conformation change and chain packing.