将可持续可再生能源收集技术与电化学水分解技术结合生成氢燃料，正成为当前解决能源危机最有前途的方法之一。要实现水的电催化分解，很大程度上取决于两极反应：氢析出反应（hydrogen evolution reaction, HER）和氧析出反应（Oxygen evolution reaction, OER），因此，开发具有低成本、高活性和耐用性的电催化剂至关重要。近来，各种各样的异质结构催化剂脱颖而出，显示出比同种单组分催化剂更优异的催化水分解性能。硫化镍Ni₃S-₂材料成本低廉合成简单，且有着潜在的电催化性能，硼酸盐阴离子掺杂是一种有效改善OER和HER的方法，掺杂后形成Ni₃S-₂ / Ni₃(BO₃)₂异质结构有望改善Ni₃S-₂的低催化性能。过渡金属硫化物 MoS₂作为备受关注的电催化材料，其析氢性能始终受到少活性位点、低导电性等因素的限制。利用金属Mo相导电性强的优点，可以合成MoS₂/Mo异质结构，作为有希望的MoS₂基电催化剂。本论文中，基于第一性原理的量子计算方法，系统研究了Ni₃S-₂ / Ni₃(BO₃)₂异质结构体系以及MoS₂/Mo异质结构体系的HER和OER电催化性质，采用H原子吸附吉布斯自由能值推测HER催化活性，采用计算所得OER吉布斯自由能能图推测其电势决定步骤和理论过电位。结果表明：（1）Ni₃S-₂/Ni₃(BO₃)₂异质结构表面HER催化活性优于单组分的催化活性，形成异质结有利于促进各组分表面的氢吸附能力向最佳值变化，以此改善整体表面的电催化活性。（2）Ni₃S-₂/Ni₃(BO₃)₂异质结构上形成的界面上有两个OER反应位点，其中一个位点的理论过电位远低于单组分Ni₃S-₂和单组分Ni₃(BO₃)₂，由此可以推测Ni₃S-₂/Ni₃(BO₃)₂异质结构体系OER催化活性较高，有望成为性能优越的OER电催化剂。（3）形成MoS₂/Mo异质结构导致Mo相基面的活性位点发生变化，而对MoS₂相基面的活性位点没有影响，同时形成的复合边缘面上，S原子为主要活性位点。（4）在四种不同构型MoS₂/Mo中，三种构型2H-MoS₂/Mo(0 0 1)，2H-MoS₂/Mo(1 1 0)和1T-MoS₂/Mo(1 1 0)均出现 ?G_H*十分接近于零的活性位点，1T-MoS₂/Mo(0 0 1)的活性位点也能够达到相比单组分MoS₂-更接近零的值，说明形成MoS₂/Mo异质结构可以很好的提升催化剂的HER活性。

Combining sustainable and renewable energy collection technologies with electrochemical water splitting technology to generate hydrogen fuel is becoming one of the most promising methods to solve the energy crisis. The electrocatalytic decomposition of water depends largely on two reactions: hydrogen evolution reaction (HER) and oxygen evolution reaction (Oxygen evolution reaction, OER). Therefore, the development of electrocatalysts with high activity and durability is crucial. Recently, various heterostructure catalysts have stood out, showing better performance in catalyzing water-splitting than single-component catalyst. Nickel sulfide (Ni₃S-₂) materials are low-cost and simple to synthesize, which have potential to be great electrocatalysis. Borate anion doping is an effective method to improve OER and HER. The resulting heterostructure Ni₃S-₂/Ni₃(BO₃)₂ is expected to improve the low electrocatalytic activity of Ni₃S-₂. Molybdenum disulfide (MoS₂) has been used as electrocatalyst material that has attracted much attention. However, its HER performance is limited by its few active sites and low conductivity. Taking advantage of the strong conductivity of the metal Mo phase, MoS₂ / Mo heterostructure can be a promising MoS2-based HER electrocatalyst. In this paper, based on the first-principles quantum calculation method, we systematically studied the HER and OER electrocatalytic properties of Ni₃S-₂/Ni₃(BO₃)₂ system and MoS₂ / Mo system, using H adsorption Gibbs free energy value to study their HER catalytic activity. And the calculated OER Gibbs free energy diagram was used to determine its rate-determing step and theoretical overpotential. The results show that: (1) The catalytic activity of HER on the surface of Ni₃S-₂/Ni₃(BO₃)₂ heterostructure is better than that of single component, because that the formation of heterojunction is conducive to change the hydrogen adsorption Gibbs free energy of each component surface to the optimal value. (2) There are two OER reaction sites on the interface area of  Ni₃S-₂/Ni₃(BO₃)₂ heterostructure, and the theoretical overpotential of one site is much lower than that of single-component Ni₃S-₂ and single-component Ni₃(BO₃)₂, it can be speculated that the Ni₃S-₂/Ni₃(BO₃)₂ heterostructure system has high OER catalytic activity which is expected to become an excellent OER electrocatalyst. (3) The formation of MoS₂/Mo heterostructure leads to changes in the active sites of the Mo-phase basal plane, but has no effect on the active sites of the MoS2-phase basal plane. At the same time, the S edge is the main active site on the composite edge surfaces. (4) Among the four different configurations of MoS₂/Mo, three configurations including 2H-MoS₂/Mo(0 0 1), 2H-MoS₂/Mo (1 1 0) and 1T-MoS₂/Mo (1 1 0) all possess active sites with ΔG_H* very close to zero, and the active site of 1T-MoS₂/Mo(0 0 1) also has ΔG_H* value closer to zero than the single component MoS₂. This shows that the formation of MoS2/Mo heterostructure can improve the HER activity of the catalyst.