Self-assembled S-scheme In_(2.77)S_(4)/K^(+)-doped g-C_(3)N_(4)photocatalyst with selective O_(2)reduction pathway for efficient H_(2)O_(2)production using water and air

The development of an efficient artificial H_(2)O_(2)photosynthesis system is a challenging work using H_(2)O and O_(2)as starting materials.Herein,3D In2.77S_(4)nanoflower precursor was in-situ deposited on K^(+)-doped g-C_(3)N_(4)(KCN)nanosheets using a solvothermal method,then In2.77S_(4)/KCN(IS/KCN)het-erojunction with an intimate interface was obtained after a calcination process.The investigation shows that the photocatalytic H_(2)O_(2)production rate of 50IS/KCN can reach up to 1.36 mmol g^(-1)h^(-1)without any sacrificial reagents under visible light irradiation,which is 9.2 times and 4.1 times higher than that of KCN and In2.77S_(4),respectively.The enhanced activity of the above composite can be mainly attributed to the S-scheme charge transfer route between KCN and In2.77S_(4)according to density functional theory calculations,electron paramagnetic resonance and free radical capture tests,leading to an expanded light response range and rapid charge separation at their interface,as well as preserving the active electrons and holes for H_(2)O_(2)production.Besides,the unique 3D nanostructure and surface hydrophobicity of IS/KCN facilitate the diffusion and transportation of O_(2)around the active centers,the energy barriers of O_(2)protonation and H_(2)O_(2)desorption steps are ef-fectively reduced over the composite.In addition,this system also exhibits excellent light harvesting ability and stability.This work provides a potential strategy to explore a sustainable H_(2)O_(2)photo-synthesis pathway through the design of heterojunctions with intimate interfaces and desired reac-tion thermodynamics and kinetics.

Novel S‐scheme 2D/2D BiOBr/g‐C_(3)N_(4)heterojunctions with enhanced photocatalytic activity

The design and construction of heterojunction photocatalysts,which possess a staggered energy band structure and appropriate interfacial contact,is an effective way to achieve outstanding photocatalytic performance.In this study,2D/2D BiOBr/g‐C_(3)N_(4)heterojunctions were successfully obtained by a convenient in situ self‐assembly route.Under simulated sunlight irradiation,99%of RhB(10 mg·L–1,100 mL)was efficiently degraded by 1.5‐BiOBr/g‐C_(3)N_(4)within 30 min,which is better than the performance of both BiOBr and g‐C_(3)N_(4),and it has superior stability.In addition,the composite also exhibits enhanced photocatalytic activity for H2 production.The enhanced activity can be attributed to the intimate interface contact,the larger surface area,and the highly efficient separation of photoinduced electron–hole pairs.Based on the experimental results,a novel S‐scheme model was proposed to illuminate the transfer process of charge carriers.This study presents a simple way to develop novel step‐scheme photocatalysts for environmental and related applications.

UV-VIS-NIR-induced extraordinary H2 evolution over W_(18)O_(49)/Cd_(0.5)Zn_(0.5)S:Surface plasmon effect coupled with S-scheme charge transfer

In this work,a novel plasmon-assisted UV-vis-NIR-driven W_(18)O_(49)/Cd_(0.5)Zn_(0.5)S heterostructure photocatalyst was obtained by a facile ultrasonic-assisted electrostatic self-assembly strategy.The hybrid exhibits extraordinary H2 evolution activity of 147.7 mmol·g^(-1)·h^(-1) at room temperature due to the efficient charge separation and expanded light absorption.Our investigation shows that the unique Step-scheme(S-scheme)charge transfer and the‘hot electron’injection are both responsible for the extraordinary H2 evolution process,depending on the wavelength of the incident light.Moreover,by accelerating the surface reaction kinetics,the activity can be further elevated to 306.1 mmol·g^(-1)·h^(-1),accompanied by a high apparent quantum yield of 45.3% at 365±7.5 nm.This work provides us a potential strategy for the highly efficient conversion of the solar energy by elaborately combining a nonstoichiometric ratio plasmonic material with an appropriate active photocatalyst.

Sustainable synthesis of high-density fuel via catalytic cascade cycloaddition reaction

The access to high-density hydrocarbon fuels from biomass for the reduction of dependence on fossil resources has been a research highlight in recent years. It is well known that cycloalkanes are the components of fuels with higher energy density than straight or branched alkanes. Herein, we developed a new catalytic pattern to synthesize dimethyltetradecahydroanthracenes(DMTHA), a kind of tricyclic alkane, from biomass-derived isoprene and p-benzoquinone via a cascade Diels-Alder reaction followed by a hydrodeoxygenation reaction. Vanadium supported on titanium dioxide(V-TiO_(2)) was applied to catalyze the cascade Diels-Alder reaction and it was disclosed that V with appropriate V^(4+)/V^(5+) ratio on the surface of TiO_(2) could activate quinones. Experimental tests showed that the heating value of final products was up to 45.7 MJ/kg. The development of new high-density fuel molecules is a long-term trend for the future renewable and sustainable fuel energy application.

An Abrasion Resistant TPU/SH-SiO_(2) Superhydrophobic Coating for Anti-Icing and Anti-Corrosion Applications

As a passive anti-icing strategy,properly designed superhydrophobic coatings can demonstrate outstanding performances.However,common preparation strategies for superhydrophobic coatings often lead to environmental pollution,high energy-consumption,high-cost and other undesirable issues.Besides,the durability of superhydrophobic coating also plagues its commercial application.In this paper,we introduced a facile and environment-friendly technique for fabricating abrasion-resistant superhydrophobic surfaces using thermoplastic polyurethane(TPU)and modified SiO_(2)particles(SH-SiO_(2)).Both materials are non-toxicity,low-cost,and commercial available.Our methodology has the following advantages:use of minimal amounts of formulation,take the most streamlined technical route,and no waste material.These advantages make it attractive for industrial applications,and its usage sustainability can be promised.In this study,the mechanical stability of the superhydrophobic surface was evaluated by linear wear test.It is found that the excellent wear resistance of the superhydrophobic coating benefits from the characteristics of raw materials,the preparation strategy,and the special structure.In anti-icing properties test,the TPU/SH-SiO_(2)coating exhibits the repellency to the cold droplets and the ability to extend the freezing time.The electrochemical corrosion measurement shows that the asprepared superhydrophobic surface has excellent corrosion resistance that can provide effective protection for the bare Q235 substrates.These results indicate that the TPU/SH-SiO_(2)coating possesses good abrasion resistance and has great potential in anti-corrosion and anti-icing applications.

S-scheme regulated Ni_(2)P-NiS/twinned Mn_(0.5)Cd_(0.5)S hetero-homojunctions for efficient photocatalytic H_(2)evolution

Effective bulk phase and surface charge separation is critical for charge utilization during the photo-catalytic energy conversion process.In this work,the ternary Ni_(2)P-NiS/twinned Mn_(0.5)Cd_(0.5)S(T-MCS)nanohybrids were successfully constructed via combining Ni_(2)P-NiS with T-MCS solid solution for visible light photocatalytic H_(2)evolution.T-MCS is composed of zinc blende Mn_(0.5)Cd_(0.5)S(ZB-MCS)and wurtzite Mn_(0.5)Cd_(0.5)S(WZ-MCS)and those two alternatively arranged crystal phases endow T-MCS with excellent bulk phase charge separation performance for the slight energy level difference between ZB-MCS and WZ-MCS.S-scheme carriers transfer route between NiS and T-MCS can accelerate the interfacial charge separation and retain the active electrons and holes,meanwhile,co-catalyst Ni_(2)P as electron receiver and proton reduction center can further optimize the H_(2)evolution reaction kinetics based on the surface Schottky barrier effect.The above-formed homo-heterojunctions can establish multiple charge transfer channels in the bulk phase of T-MCS and interface of T-MCS and Ni_(2)P-NiS.Under the synergistic effect of twinned homojunction,S-scheme heterojunction,and Schottky barrier,the ternary Ni_(2)P-NiS/T-MCS com-posite manifested an H_(2)production rate of 122.5 mmol h^(-1)g^(-1),which was 1.33,1.24,and 2.58 times higher than those of the NiS/T-MCS(92.4 mmol h^(-1)g^(-1)),Ni_(2)P/T-MCS(98.4 mmol h^(-1)g^(-1)),and T-MCS(47.5 mmol h^(-1)g^(-1)),respectively.This work demonstrates a promising strategy to develop efficient sul-fides photocatalyst toward targeted solar-driven H_(2)evolution through homo-heterojunction engineering.

模板遗传实现纳微双尺度有序化碳单元及其在紧凑电容储能中的应用

紧凑型超级电容器需要具有高体积能量和功率密度的高密度碳.然而,大多数传统的密度提升方案都是基于孔隙压缩,导致提高体积性能的同时过多地牺牲倍率性能.在此,本研究从碳单元有序堆叠的相反角度出发,提出了一种通过调节模板形貌在纳米和微米双尺度上压缩碳单元之间剩余孔隙的新策略(即一级碳纳米笼和二级由碳纳米笼组成的类碟状组装体的双尺寸排序).优化的纳微有序碳单元的电极密度高达1.08 g cm^(-3)(是商业活性炭的两倍);在离子液体中表现了创纪录的体积能量密度(79 Wh L^(-1))和功率容量(31 kW L^(-1)),以及出色的稳定性(>30,000次循环)和理想的库仑效率(~100%).即使在商业级电极厚度下,其可用的最大堆叠功率密度仍然高达12 kW L^(-1),远高于大多数报道的致密碳.如此出色的体积性能使其在同时需要高体积能量和功率密度的领域具有巨大潜力.