过渡金属硫族化合物（TMDs）因其独特可调的电子结构及物理、化学性质，成为能源转换催化剂中热门的研究对象。通过相调控，此类材料的金属性相态有较高的电解水析氢催化本征活性，同时优良的导电性有利于催化过程中的电子传输；其半导体性相态的边缘有较高的CO2还原活性，并且能够抑制竞争反应的发生。然而相比贵金属材料，其性能仍有差距，同时稳定性是实用化进程中的关键科学问题。本论文以MoS2、NiSe2为主要研究对象，通过探索溶剂热合成新方法，基于相调控实现了高活性、稳定复合电催化剂的构筑，并通过复杂结构和组分的设计实现了性能的提升，并采用多种表征方法从多组分协同效应、界面性质等方面揭示构效关系，最终达到电催化性能优化的目的，对解决能源危机和环境问题具有重要意义。 （1）首次提出一种新型溶剂热合成策略以诱导MoS2完全相变，即利用水合肼的给电子作用，以Ni-Co氢氧化物为前驱体实现了1T MoS2与非晶态Ni-Co配合物多孔复合材料的构筑。该复合催化剂展示出优异的全水解性能，同时以非晶态Ni-Co配合物来稳定1T MoS2的方法为稳定亚稳态TMDs材料提供新的思路。 （2）采用上述合成策略，系统化设计并构筑了1T’ MoS2/(Co, Fe, Ni)9S8复合纳米管阵列。多组分间的协同效应提升了材料催化本征活性，1T’ MoS2的金属性增强了材料的导电性，多孔结构和粗糙表面增大了活性位点数量，阵列结构超疏气及超亲水的表面性质促进了催化传质。该复合催化剂展示出超高的全水解效率，原位结构表征展现了复合材料中1T’ MoS2卓越的电催化稳定性。 （3）以ZIF-67为反应模板和碳源，在高温还原气氛下合成了氮掺杂碳复合2H MoS2多级中空纳米笼。大量暴露的2H MoS2边缘为CO2电还原提供活性中心，同时两组分间的电子转移提升了催化剂的本征催化活性。碳材料增强了催化剂的导电性，中空、多孔结构的构筑增大了活性位点的数量，促进了催化传质。该复合催化剂获得了超高的CO2电催化还原活性，CO的选择性达到92.68%。 （4）利用常压体系热注入法以及高压封闭体系溶剂热法在乙二醇体系中两步合成了非晶态NiOx纳米颗粒修饰的超细NiSe2纳米线复合材料。第二组分非晶态NiOx不仅为全水解催化提供更多活性位点，而且为本征活性中心NiSe2提供保护作用，避免其因被氧化而失活。复合催化剂展现了较好的全水解催化活性和超高的稳定性，拓宽了过渡金属二硒化物的应用范围。该工作重点探索了复合催化剂中第二组分的功效，为此类材料在电催化领域的发展带

Transition metal dichalcogenides (TMDs) have been regarded as one of the most significant materials for energy conversion catalysis due to unique and tunable electronic structures as well as physical and chemical properties. The phase of this category of material can be engineered for investigation purposes, demonstrates that metallic 1T phase possesses high intrinsic activity for hydrogen evolution reaction (HER), and superb electrical conductivity facilitates charge transfer during electrocatalysis. While semiconducting 2H phase identifies remarkable performance of edge sites for electrochemical CO2 reduction reaction (CO2RR), impeding the competing HER reaction. However, compared to noble metal-based electrocatalysts, TMDs show poorer performances and their stability can be considered as the key scientific fundamental in the process of practical applications. MoS2 and NiSe2 are the main investigation objectives and utilized for the construction of hybrid nanostructures and compositions through novel solvothermal synthetic strategies with phase engineering. The enhancement of electrocatalytic performance has been achieved by the design of complicated structures and compositions. A variety of characterizations for synergistic effects of multi-components, interfacial properties and etc. have been carried out to elucidate the structure-function relationship, thus contributing to optimization of electrocatalytic performances. These achievements play an essential role in tackling energy crisis and environmental issues. (1) We firstly proposed a novel solvothermal strategy to realize complete phase transition of MoS2 and obtained porous hybrid nanostructure comprised of 1T MoS2 and amorphous Ni-Co complexes with Ni-Co hydroxides as precursors through electron-donating effect of hydrazine hydrate. The hybrid electrocatalyst exhibited splendid catalytic performances for overall water splitting (OWS) as both anode and cathode. In this system, amorphous Ni-Co complexes can stabilize 1T MoS2 during electrocatalysis, which opens up a new road for the stabilization on metastable phase of TMDs materials. (2) Based on the above synthetic strategy, we systematically designed and constructed a hybrid nanotube-array electrode constituted by 1T’ MoS2 and (Co, Fe, Ni)9S8. The advantages of this hybrid electrode for OWS electrocatalysis are demonstrated as follows. The synergistic effects of multi-components improve the intrinsic activity for OWS. The metallic feature of 1T’ MoS2 promotes the electrical conductivity of the electrode. Porous nanostructures and uneven surface of the nanotubes enhance the density of catalytic active sites. Besides, superaerophobicity and superhydrophilicity of the surface of the nanoarray architectures facilitate the mass transfer process of water splitting electrocatalysis. The hybrid nanotube arrays show ultrahigh efficiency and excellent stability for OWS. In situ structural characterizations demonstrate the fascinating electrochemical stability of as-prepared 1T’ MoS2. (3) The hierarchical hollow cages comprised of edge-exposed 2H MoS2 and N-doped carbon have been synthesized by thermal reduction with ZIF-67 rhombic dodecahedrons as template and carbon source at a high temperature. A large quantity of exposed edges of 2H MoS2 provide active centers for CO2RR and charge transfer between the two components promotes the intrinsic activity of the hybrid electrocatalyst. Carbon hybridization improves electrical conductivity. Porous hollow structure enhances specific surface area and facilitates mass transfer process of electrocatalysis. We have acquired highly active and robust hybrid electrocatalyst for CO2RR, which can achieve 92.68% of Faradaic efficiency for CO production. (4) We successfully prepared amorphous NiOx nanoparticles (NPs) decorated NiSe2 ultrathin nanowires (UNWs) in ethylene glycol solvent system with two-step hot-injection method in an atmospheric pressure reaction system and subsequent high-pressure solvothermal method in a sealed system. The secondary component, amorphous NiOx NPs, did not only provides more catalytic active sites for OWS, but it also protects the inherent active center, NiSe2 UNWs, from further oxidation during electrocatalysis for avoiding inactivation. The hybrid electrocatalyst displayed highly active and ultra-stable performances for OWS, which expands the applied range of transition metal diselenides. This work mainly explores the functionality of secondary component in the hybrid material, bringing new opportunities of this category of material in electrocatalysis.