随着环境问题的日益严重，我国政府提出“碳达峰”、“碳中和”的“双碳”目标。氢能作为重要的二次能源具有来源广泛、能量密度大、热值高、清洁可再生等诸多优势。在众多的制氢技术中，电解水制氢被认为是最安全、绿色的途径。然而电解水制氢过程中存在反应过电位高、催化剂稳定性差等关键问题。在电解水制氢过程中，与二电子反应的HER过程相比，四电子的OER过程需要更高的过电位。因此，为了实现高效率、低能耗的电解水制氢过程，寻找合适、高效且稳定的OER催化剂成为了水裂解制氢研究的一个重要目标。目前，在众多催化剂中，镍铁水滑石(NiFe-LDHs)由于其原料廉价易得、结构高度可控以及优异的OER本征活性，受到研究人员的广泛关注。通过异质原子掺杂可以有效地调控层板结构，优化活性中心的电子结构，充分利用掺杂离子的诱导作用，可以产生新的耦合作用，提升催化活性和稳定性。本论文以NiFe-LDHs为模型催化剂，通过引入廉价过渡金属元素Cu、Mn，确认构效关系，调控催化活性，具体研究内容如下：

(1) 通过一步水热法，在NiFe-LDHs层板中引入Cu(Ⅱ)，利用Cu(Ⅱ)中t_2g和E_g轨道结构的扭曲所引发的Jahn-Teller效应，优化和调控NiFe-LDHs的层板电子结构。在1.0 M KOH的条件下进行测试，当电流密度为10 mA cm^-2时，Cu-NiFe-LDHs过电位仅为331 mV，相较于同条件下的初始的NiFe-LDHs降低了92 mV，表现出优异的电催化活性。根据实验和理论计算结果表明，Cu(Ⅱ)的Jahn-Teller效应可以有效影响了Fe³⁺的电荷密度，促使Fe³⁺的配体层强度由弱场向强场转变，改变了层板的电子活性，有效地降低带隙，提升层板的导电性，表现出更好的OER活性。

(2) 借由上一步的研究思路，通过一步水热法，在反应的过程中引入Mnⁿ⁺，利用锰离子的变价特性，在NiFe-LDHs层板中引入变价Mnⁿ⁺，诱导调控活性中心活性中心的电子分布的调控。Mnⁿ⁺的引入的引入有效地提高了层板中活性Ni³⁺的比例，有助于暴露更多的有效活性位点。在反应过程中，Ni-Fe-Mn多位点协同效应，可以有效地提高了电催化活性。在1.0 M KOH的条件下，在电流密度为1.0 mA cm^-2时，Mn-NiFe-LDHs样品的过电位（267mV）低于NiFe-LDHs（288mV），在电流密度为10 mA cm^-2下Mn-NiFe-LDHs的过电位（332mV）低于NiFe-LDHs（374mV）。同时该材料表现出优异的电催化稳定性。

As secondary energy, hydrogen energy has many advantages, such as wide source, large specific energy density, high calorific value, clean and renewable. With the development of hydrogen energy industry in the world, especially the double carbon target of "carbon peak" and "carbon neutralization" put forward by our government, speeding up the development of hydrogen energy industry has become the need of the development of the times. Among the many methods of hydrogen production, electrolytic water is considered to be the safest and green way to prepare hydrogen. However, there is a high reaction overpotential in the electrolytic water process. Compared with the hydrogen evolution reaction of the two electrons, the oxygen evolution reaction of the four electrons requires a higher overpotential. Therefore, in order to realize the low energy consumption and high efficiency electrolytic water hydrogen production process, reducing the oxygen evolution reaction (OER) overpotential by finding suitable catalysts has become an important research direction for hydrogen production in electrolytic water. at present, among many catalysts, NiFe-LDHs have been widely concerned by researchers because of its great development potential, low cost, high controllability of structure and good activity. Heteroatom doping can effectively regulate the electronic structure of laminates and active sites, which is helpful to explore the structure-activity relationship in the optimization of OER reaction. At the same time, the induction of doped ions can be fully utilized to produce new coupling effects and optimize their electrochemical performance. Therefore, using NiFe-LDH as the model catalyst, the following studies were carried out by introducing cheap transition metal elements Mn 、Cu, regulating their properties by structural changes:

(1) By one-step hydrothermal method, Cu(Ⅱ) is introduced into NiFe-LDHS laminae, and the electronic structure of NiFe-LDHS laminae is optimized and regulated by the Jahn-Teller effect caused by the distortion of e_g and t_2g orbit structures. When the current density is 10 mA cm^-2, the overpotential of Cu-NiFe-LDHs is only 331 mV, which is reduced by 92 mV compared with the NiFe-LDHs under the same condition, showing excellent electrochemical catalytic activity. According to the experimental and theoretical calculation results, the Jahn-Teller effect of Cu(Ⅱ) can effectively affect the charge density of Fe³⁺, promote the strength of Fe³⁺ ligand layer from weak field to strong field, change the electronic activity of the laminate, effectively reduce the band gap, improve the electrical conductivity of the laminate, and show better OER activity.

(2) Based on the previous research idea, Mnⁿ⁺ was introduced into the reaction process through one-step hydrothermal method, and the valence property of manganese ions was used to introduce Mnⁿ⁺ into the NiFe-LDHs layer to induce the regulation of the electron distribution of the active center. The introduction of Mnⁿ⁺ can effectively increase the proportion of active Ni³⁺ in the laminate, and help to expose more active sites. In the reaction process, Ni-Fe-Mn multi-site synergistic effect can effectively improve the electrochemical activity. Under the condition of 1.0 M KOH and the current density of 1.0 mA cm^-2, the overpotential (267mV) of Mn-NiFe-LDHs sample is lower than that of NiFe-LDHs (288mV). At the current density of 10 mA cm^-2, the overpotential of Mn-NiFe-LDHs (332mV) is lower than that of NiFe-LDHs (374mV). At the same time, the material showed excellent electrocatalytic stability.