MoTe2的结构调控及其电催化产氢和储能应用进展

开发能量转化和存储的高性能电极材料对于新能源利用和储能元件的改进至关重要.设计合成高表面积和较大层间距的二维电极材料是提高电催化活性和储能性能的有效方法.近年来,在过渡金属硫族化合物材料合成快速发展的基础上,MoTe₂更大的层间距和较好的导电性使其在各个领域得到了广泛的研究,其中物相工程、形貌控制和缺陷工程技术逐渐被用于提升MoTe₂的电催化产氢和储能性能.这篇综述对MoTe₂在电催化产氢以及能量存储方面的研究进展进行了总结,展示了MoTe₂较高的电催化产氢活性和优异的储能性能,是一种具有发展潜力的二维材料.与此同时,就该领域存在的问题和应用前景进行了展望.     

柔性复合织物电极Graphene/Cotton和MnO2/Graphene/Cotton的合成及在电化学电容器中的应用

通过热还原法成功地制备出了柔性复合织物电极石墨烯/棉布(graphene/cotton)。热还原条件对电极的导电性能具有较大的影响。导电柔性织物电极graphene/cotton特有的多级结构使其既有利于进一步负载膺电容材料,又有利于电子和电解质离子的传输与扩散。通过电化学沉积方法,利用导电柔性织物电极graphene/cotton进一步制备出了电极MnO₂/graphene/cotton。利用扫描电子显微镜(SEM),傅里叶变换红外(FTIR)光谱,四探针测试法等表征技术对电极的结构进行了较为详细的表征。结果表明电极MnO₂/graphene/cotton的比电容可以达到536 F·g^-1。良好的电化学性能和柔性使得此类电极在柔性储能材料应用中具有极大的应用前景。     

血红蛋白在二氧化铈修饰电极上的直接电化学

将二氧化铈(CeO₂)与酶复合修饰电极, 采用循环伏安法研究了血红蛋白(Hb)在CeO₂修饰的玻碳电极上的电化学行为. 实验表明, 固定在CeO₂材料上的Hb, 不仅能有效地与电极表面进行直接电子转移, 而且能够保持其生物催化活性. 制得的Nafion/CeO₂/Hb/GC修饰电极的电子传递速率k_s为(0.68±0.09) s^－1, 对H₂O₂的检测限为1.013 μmol•L^－1, 重现性和稳定性较好. CeO₂在实验中体现出一定的生物相容性, 起到了促进Hb与电极之间进行直接电子传递的作用. CeO₂修饰电极进行蛋白质直接电化学测定以及酶生物电催化的成功实践, 为稀土氧化物材料在电化学传感领域中的应用开辟了思路.     

碳布负载氢氧化镍电极材料的合成及其电容性能分析——推荐一个综合化学实验

作为超级电容器的电极材料,Ni(OH)₂具有理论比电容高、来源丰富、环境友好等优点,但较低的电导率影响了其实际性能。解决该问题的一种有效方法是在碳布导电基底上原位生长Ni(OH)₂薄膜。以此为基础设计综合化学实验,通过Ni(OH)₂/碳布薄膜电极的制备、表征及电化学性能测试,使学生进一步理解化学平衡原理在材料合成中的应用,了解材料的基本表征方法,掌握循环伏安法、恒流充放电法等电化学分析方法在实际测试中的运用与解析,从而达到巩固电化学理论知识、培养学生的实验技能、提高学生综合实验能力的目的。本实验的开展还可以帮助学生了解储能领域的科技前沿,激发学生的科研兴趣,培养学生的科研创新意识,适合在大学化学实验中推广应用。     

二氧化锰/石墨烯纸电极的制备及其电化学性能

通过电化学法使溶液中的Mn²⁺电解氧化为MnO₂,沉积复合在石墨烯片膜上,形成由MnO₂/石墨烯复合材料构成的纸电极。 采用X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)、循环伏安(CV)和恒流放电等技术手段对纸电极材料的结构、形貌以及电化学性能进行了研究。 结果表明,MnO₂球形颗粒均匀地沉积在石墨烯片膜上,形成了厚度45 μm的纸电极,经过380 ℃煅烧后,纸电极中的MnO₂晶型由γ-MnO₂转化为β/γ-MnO₂混合晶型,是良好的柔性Li/MnO₂电池的电极材料。 MnO₂/石墨烯纸电极在室温下0.1C放电容量达269 mA·h/g,而且电化学阻抗低、柔韧性好。     

基于过渡金属硫化物/还原氧化石墨烯复合物的高性能超级电容器

组装高能量密度的非对称超级电容器需要使用比电容大、 体积变化小且循环稳定性好的电极材料. 过渡金属硫化物(TMSs)与纳米碳材料的复合物是此类电极材料之一. 采用水热法合成了由Cu-Mo硫化物在微波剥离的还原氧化石墨烯表面生长的复合材料(CuS-MoS₂/MErGO). 此复合材料在电流密度为2 A/g时具有高达861.5 F/g的比电容和良好的循环稳定性. 将1.6 V的电池电压施加在由NiS/MErGO为正极, CuS-MoS₂/MErGO为负极组装成的不对称超级电容器上时, 该电容器的功率密度为1.28 kW/kg, 且能量密度保持为54.2 W·h·kg^-1. 结果表明, TMS复合材料是一种很有前途的高性能电化学储能材料, 尤其是用于非对称超级电容器的组装.     

表面钒修饰对α-Fe2O3材料光电化学性能的增强作用

对半导体材料进行表面化学修饰或改性,是提高其光催化活性、有效利用光能的一种重要措施.本文结合水热化学法、化学池沉积和后续热处理等,分别制备了未修饰α-Fe₂O₃和钒修饰的α-Fe₂O₃光电极材料.利用X射线粉末衍射(XRD)谱和紫外-可见漫反射光谱(UV-Vis-DRS)技术分析表征了材料的晶相结构、化学组成和光谱吸收等固体物理化学性能;利用光电流测量和电化学交流阻抗谱(EIS)实验技术,并基于1 mol·L^-1NaOH (pH 13.6)中的光电化学水分解反应,研究了钒修饰对α-Fe₂O₃材料光电化学性能的增强作用.结果表明,与未修饰的Fe₂O₃材料相比,钒修饰α-Fe₂O₃样品出现FeVO₄的XRD特征峰,但临界光吸收波长未发生红移;钒修饰使Fe₂O₃材料的光电流增大4-5倍、光生载流子在电极表面的复合几率降低了3/4-4/5、电极表面电荷传递速率(表观一级速率常数)明显提高.结合Fe₂O₃/溶液界面半导体能带模型和有关研究结果,分析了研究体系的界面电荷动力学传输过程以及钒修饰使α-Fe₂O₃材料光电化学性能增强的原因.     

杂多酸/聚苯胺/二氧化锰复合材料的制备及其电化学性能研究

使用磷钨酸(PW₁₂)为苯胺(AN)单体聚合提供酸环境,合成聚苯胺(PANI),通过原位聚合法制备出不同比例的PW₁₂/PANI/MnO₂复合材料。通过红外光谱(FT-IR)、X射线衍射(XRD)和扫描电镜(SEM)对复合材料电极材料的结构和形貌进行表征,利用电化学工作站测试复合材料的电化学性能。结果表明,制备出的复合材料呈现以下优点,例如明显的多孔结构,较大的比表面积,材料的团聚现象也得到了明显的改善,复合材料的比电容达到493.29 F/g左右,说明经过掺杂的复合材料的电化学性能相对于单一赝电容材料(聚苯胺,314.27 F/g)有了明显的提升,合成的三元纳米复合材料具有作为电极材料的潜力,可用于下一代高速率储能系统。     

锂离子电池SnS2基负极材料

随着应用范围的逐渐扩大,锂离子电池对具有高比容量、长循环寿命以及优异倍率性能的新型正负极材料的需求日益迫切。SnS₂材料因具有独特的层状结构和高的理论比容量而被视作潜在的高比容量负极材料,但其也存在首次不可逆容量较大、导电率低、充放电过程中体积变化较大等问题。本文综述了SnS₂负极材料的研究历程以及最新研究进展,介绍了SnS₂负极材料的基本性质,具体论述了SnS₂电化学性能改进的相关措施,主要包括控制纳米SnS₂微观形貌、制备SnS₂/C及SnS₂/氧化物复合材料、掺杂、一体化电极以及优化粘结剂等。文章同时总结了水热（溶剂热）法各工艺参数（原料种类、浓度、比例、溶液pH值、水热温度及时间等）对制备SnS₂纳米材料及SnS₂/C复合材料形貌结构及电化学性能的影响,并对目前SnS₂材料仍然存在的问题进行了分析。研究表明,通过制备片状、花状等高比表面积的SnS₂纳米材料,可明显提升其循环性能;将石墨烯等碳材料与SnS₂复合,有助于提高材料的结构稳定性及导电性,进而改善电极的循环及倍率性能。经工艺优化后的SnS₂/graphene复合材料具有高的比容量（大于1000 mAh/g）、稳定的循环性能和优秀的倍率特性,是一种非常有研究价值的高比容量锂离子电池负极材料。     

Ni(OH)2修饰的三聚氰胺泡沫用于可压缩超级电容器电极

通过化学镀和电化学镀的方法制备了一种Ni(OH)₂电化学活性材料修饰三聚氰胺泡沫(MF)可压缩骨架的超级电容器电极材料MF/Ni(OH)₂。MF/Ni(OH)₂可压缩电极材料表现出最佳的电容性能,例如循环稳定性(即使在40 mA/cm^-3的电流密度下经过2000次充放电循环后,可压缩电极仍能保持90.63%的初始电容)和可压缩稳定性(即使在压缩率为50%时,仍具有97.88%的电容保持率)。层状可压缩超级电容器由MF/Ni(OH)₂弹性材料作为阳极,镍/碳(Ni/C)为阴极以及实验室中常用的滤纸作隔膜材料组成。这种超级电容器装置在不同的压缩下表现出良好的电化学性能和优异的压缩稳定性。最后,使用可压缩的超级电容器来点亮LED灯,以展示其在柔性电子设备中的应用。这些优化的电化学和机械性能表明MF/Ni(OH)₂可作为可压缩超级电容器的应用中的候选电极。     

Bandgap engineering of tetragonal phase CuFeS2 quantum dots via mixed-valence single-atomic Ag decoration for synergistic Cr(VI) reduction and RhB degradation

Bandgap engineering through single-atom site binding on semiconducting photocatalyst can boost the intrinsic activity, selectivity, carrier separation, and electron transport. Here, we report a mixed-valence Ag(0) and Ag(I) single atoms co-decorated semiconducting chalcopyrite quantum dots (Ag/CuFeS₂ QDs) photocatalyst. It demonstrates efficient photocatalytic performances for specific organic dye (rhodamine B, denoted as RhB) as well as inorganic dye (Cr(VI)) removal in water under natural sunlight irradiation. The RhB degradation and Cr(VI) removal efficiencies by Ag/CuFeS₂ QDs were 3.55 and 6.75 times higher than those of the naked CuFeS₂ QDs at their optimal pH conditions, respectively. Besides, in a mixture of RhB and Cr(VI) solution under neutral condition, the removal ratio has been elevated from 30.2% to 79.4% for Cr(VI), and from 95.2% to 97.3% for RhB degradation by using Ag/CuFeS₂ QDs after 2 h sunlight illumination. The intrinsic mechanism for the photocatalytic performance improvement is attributed to the narrow bandgap of the single-atomic Ag(I) anchored CuFeS₂ QDs, which engineers the electronic structure as well as expands the optical light response range. Significantly, the highly active Ag(0)/CuFeS₂ and Ag(I)/CuFeS₂ effectively improve the separation efficiency of the carriers, thus enhancing the photocatalytic performances. This work presents a highly efficient single atom/QDs photocatalyst, constructed through bandgap engineering via mixed-valence single noble metal atoms binding on semiconducting QDs. It paves the way for developing high-efficiency single-atom photocatalysts for complex pollutions removal in dyeing wastewater environment.     

Mechanochemistry for Energy Materials: Impact of High-Energy Milling on Chemical,Electric and Thermal Transport Properties of Chalcopyrite CuFeS2 Nanoparticles

Chalcopyrite CuFeS₂, a semiconductor with applications in chemical sector and energy conversion engineering, was synthetized in a planetary mill from elemental precursors. The synthesis is environmentally friendly, waste-free and inexpensive. The synthesized nano-powders were characterized by XRD, SEM, EDX, BET and UV/Vis techniques, tests of chemical reactivity and, namely, thermoelectric performance of sintered ceramics followed. The crystallite size of ∼13 nm and the strain of ∼17 were calculated for CuFeS₂ powders milled for 60, 120, 180 and 240 min, respectively. The evolution of characteristic band gaps, Eg, and the rate constant of leaching, k, of nano-powders are corroborated by the universal evolution of the parameter S_BET/X (S_BET-specific surface area, X-crystallinity) introduced for complex characterization of mechanochemically activated solids in various fields such as chemical engineering and/or energy conversion. The focus on non-doped semiconducting CuFeS₂ enabled to assess the role of impurities, which critically and often negatively influence the thermoelectric properties.     

The influence of magnetic ordering on the electronic energy structure of CuFeS<Subscript>2</Subscript>

The modified LAPW+lo method with Wien2k software package was used to calculate the electronic energy structure of CuFeS₂ as a component of chalcopyrite. CuFeS₂ was found to be a conductor in the absence of antiferromagnetic ordering. Antiferromagnetic ordering in (001) layers leads to appearance of an energy gap and transforms CuFeS₂ into a semiconductor. In the GGA+U approximation, E g ≈ 0.75 eV was achieved for U = 6 eV, which is close to experimental value.     

Long-Life,High-Rate Rechargeable Lithium Batteries Based on Soluble Bis(2-pyrimidyl) Disulfide Cathode

Organosulfides are promising candidates as cathode materials for the development of electric vehicles and energy storage systems due to their low-cost and high capacity properties. However, they generally suffer from slow kinetics because of the large rearrangement of S−S bonds and structural degradation upon cycling in batteries. In this paper, we reveal that soluble bis(2-pyrimidyl) disulfide (Pym₂S₂) can be a high-rate cathode material for rechargeable lithium batteries. Benefiting from the superdelocalization of pyrimidyl group, the extra electrons prefer to be localized on the π* (pyrimidyl group) than σ* (S−S bond) molecular orbitals initially, generating the anion-like intermedia of [Pym₂S₂]²⁻ and thus decreasing the dissociation energy of the S−S bond. It makes the intrinsic energy barrier of dissociative electron transfer depleted, therefore the lithium half cell exhibits 2000 cycles at 5 C. This study provides a distinct pathway for the design of high-rate, long-cycle-life organic cathode materials.     

2020 roadmap on two-dimensional materials for energy storage and conversion

Energy storage and conversion have attained significant interest owing to its important applications that reduce CO₂ emission through employing green energy. Some promising technologies are included metal-air batteries, metal-sulfur batteries, metal-ion batteries, electrochemical capacitors, etc. Here, metal elements are involved with lithium, sodium, and magnesium. For these devices, electrode materials are of importance to obtain high performance. Two-dimensional (2D) materials are a large kind of layered structured materials with promising future as energy storage materials, which include graphene, black phosporus, MXenes, covalent organic frameworks (COFs), 2D oxides, 2D chalcogenides, and others. Great progress has been achieved to go ahead for 2D materials in energy storage and conversion. More researchers will join in this research field. Under the background, it has motivated us to contribute with a roadmap on ‘two-dimensional materials for energy storage and conversion.     

Molybdenum Disulfide Based Nanomaterials for Rechargeable Batteries

The rapid development of electrochemical energy storage systems requires new electrode materials with high performance. As a two-dimensional material, molybdenum disulfide (MoS₂) has attracted increasing interest in energy storage applications due to its layered structure, tunable physical and chemical properties, and high capacity. In this review, the atomic structures and properties of different phases of MoS₂ are first introduced. Then, typical synthetic methods for MoS₂ and MoS₂-based composites are presented. Furthermore, the recent progress in the design of diverse MoS₂-based micro/nanostructures for rechargeable batteries, including lithium-ion, lithium-sulfur, sodium-ion, potassium-ion, and multivalent-ion batteries, is overviewed. Additionally, the roles of advanced in situ/operando techniques and theoretical calculations in elucidating fundamental insights into the structural and electrochemical processes taking place in these materials during battery operation are illustrated. Finally, a perspective is given on how the properties of MoS₂-based electrode materials are further improved and how they can find widespread application in the next-generation electrochemical energy-storage systems.     

Synergistic Catalysis of SnO2/Reduced Graphene Oxide for VO2+/VO2+ and V2+/V3+ Redox Reactions

In spite of their low cost, high activity, and diversity, metal oxide catalysts have not been widely applied in vanadium redox reactions due to their poor conductivity and low surface area. Herein, SnO₂/reduced graphene oxide (SnO₂/rGO) composite was prepared by a sol–gel method followed by high-temperature carbonization. SnO₂/rGO shows better electrochemical catalysis for both redox reactions of VO²⁺/VO₂⁺ and V²⁺/V³⁺ couples as compared to SnO₂ and graphene oxide. This is attributed to the fact that reduced graphene oxide is employed as carbon support featuring excellent conductivity and a large surface area, which offers fast electron transfer and a large reaction place towards vanadium redox reaction. Moreover, SnO₂ has excellent electrochemical activity and wettability, which also boost the electrochemical kinetics of redox reaction. In brief, the electrochemical properties for vanadium redox reactions are boosted in terms of diffusion, charge transfer, and electron transport processes systematically. Next, SnO₂/rGO can increase the energy storage performance of cells, including higher discharge electrolyte utilization and lower electrochemical polarization. At 150 mA cm⁻², the energy efficiency of a modified cell is 69.8%, which is increased by 5.7% compared with a pristine one. This work provides a promising method to develop composite catalysts of carbon materials and metal oxide for vanadium redox reactions.     

Laser-Induced Interdigital Structured Graphene Electrodes Based Flexible Micro-Supercapacitor for Efficient Peak Energy Storage

The rapidly developing demand for lightweight portable electronics has accelerated advanced research on self-powered microsystems (SPMs) for peak power energy storage (ESs). In recent years, there has been, in this regard, a huge research interest in micro-supercapacitors for microelectronics application over micro-batteries due to their advantages of fast charge–discharge rate, high power density and long cycle-life. In this work, the optimization and fabrication of micro-supercapacitors (MSCs) by means of laser-induced interdigital structured graphene electrodes (LIG) has been reported. The flexible and scalable MSCs are fabricated by CO₂-laser structuring of polyimide-based Kapton ^® HN foils at ambient temperature yielding interdigital LIG-electrodes and using polymer gel electrolyte (PGE) produced by polypropylene carbonate (PPC) embedded ionic liquid of 1-ethyl-3-methyl-imidazolium-trifluoromethansulphonate [EMIM][OTf]. This MSC exhibits a wide stable potential window up to 2.0 V, offering an areal capacitance of 1.75 mF/cm² at a scan rate of 5.0 mV/s resulting in an energy density (E_a) of 0.256 µWh/cm² @ 0.03 mA/cm² and power density (P_a) of 0.11 mW/cm² @0.1 mA/cm². Overall electrochemical performance of this LIG/PGE-MSC is rounded with a good cyclic stability up to 10,000 cycles demonstrating its potential in terms of peak energy storage ability compared to the current thin film micro-supercapacitors.     

Silica-Derived Nanostructured Electrode Materials for ORR,OER, HER,CO2RR Electrocatalysis,and Energy Storage Applications: A Review**

Silica-derived nanostructured catalysts (SDNCs) are a class of materials synthesized using nanocasting and templating techniques, which involve the sacrificial removal of a silica template to generate highly porous nanostructured materials. The surface of these nanostructures is functionalized with a variety of electrocatalytically active metal and non-metal atoms. SDNCs have attracted considerable attention due to their unique physicochemical properties, tunable electronic configuration, and microstructure. These properties make them highly efficient catalysts and promising electrode materials for next generation electrocatalysis, energy conversion, and energy storage technologies. The continued development of SDNCs is likely to lead to new and improved electrocatalysts and electrode materials. This review article provides a comprehensive overview of the recent advances in the development of SDNCs for electrocatalysis and energy storage applications. It analyzes 337,061 research articles published in the Web of Science (WoS) database up to December 2022 using the keywords “silica”, “electrocatalysts”, “ORR”, “OER”, “HER”, “HOR”, “CO₂RR”, “batteries”, and “supercapacitors”. The review discusses the application of SDNCs for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO₂RR), supercapacitors, lithium-ion batteries, and thermal energy storage applications. It concludes by discussing the advantages and limitations of SDNCs for energy applications.     

Photocatalytic CO2 Reduction Using TiO2-Based Photocatalysts and TiO2 Z-Scheme Heterojunction Composites: A Review

Photocatalytic CO₂ reduction is a most promising technique to capture CO₂ and reduce it to non-fossil fuel and other valuable compounds. Today, we are facing serious environmental issues due to the usage of excessive amounts of non-renewable energy resources. In this aspect, photocatalytic CO₂ reduction will provide us with energy-enriched compounds and help to keep our environment clean and healthy. For this purpose, various photocatalysts have been designed to obtain selective products and improve efficiency of the system. Semiconductor materials have received great attention and have showed good performances for CO₂ reduction. Titanium dioxide has been widely explored as a photocatalyst for CO₂ reduction among the semiconductors due to its suitable electronic/optical properties, availability at low cost, thermal stability, low toxicity, and high photoactivity. Inspired by natural photosynthesis, the artificial Z-scheme of photocatalyst is constructed to provide an easy method to enhance efficiency of CO₂ reduction. This review covers literature in this field, particularly the studies about the photocatalytic system, TiO₂ Z-scheme heterojunction composites, and use of transition metals for CO₂ photoreduction. Lastly, challenges and opportunities are described to open a new era in engineering and attain good performances with semiconductor materials for photocatalytic CO₂ reduction.