化石燃料的日渐枯竭引发了绿色可再生能源储存与转化技术的研究。锌-空气电池（Zinc-Air Batteries, ZABs）由于环境友好性、高效、长时运行能力及高能量密度等特点被认为是最具前景的能源转化装置。但ZABs在实际应用中仍面临由于ORR和OER过程中缓慢的电子转移动力学造成的能量转换效率低、稳定性差等问题。目前，Pt基催化剂及RuO₂催化剂分别是最具ORR活性和OER活性的催化剂，但其昂贵又稀少的缺点限制了它们的广泛应用。因此，开发高效、低成本的非贵金属ORR/OER催化剂对于推动锌-空气电池的发展具有十分重要的意义。本论文以石墨烯为催化剂载体，金属有机骨架为活性金属来源，通过配位组装和原位生长等方法制备得到一系列过渡金属-氮-碳（M-N-C）纳米催化剂，并研究了系列材料的ORR及OER性能。具体研究内容如下：

（1）以氧化石墨烯为催化载体，通过水热条件下氧化石墨烯（GO）、Fe³⁺及单宁酸（TA）之间的配位组装诱导Fe-TA@GO的形成，进而以含氮量高的脲作为氮源，经一步碳化制得具有核-壳结构的纳米Fe/C催化剂（Fe/Fe₃C@NC-Gs）。对材料的表征与测试表明：Fe/Fe₃C@NC-Gs具有独特的核-壳结构、丰富的介孔结构、大的表面积及高效的氮掺杂。铁核和石墨壳的紧密接触有利于调节电子密度，促进电子由铁核向碳壳的转移。同时，碳壳起到对金属物种Fe/Fe₃C的保护和限域作用，可以有效防止碱性介质对活性物种的腐蚀，也有利于避免高温碳化过程中金属物种的团聚。在碱性条件下的电化学测试表明：Fe/Fe₃C@NC-G-2具有0.97 V的初始电位和0.88 V的半波电位，均高于商用的Pt/C催化剂。此外，当Fe/Fe₃C@NC-G-2作为ORR催化剂使用时，其具有比商用Pt/C催化剂还要高的稳定性和优异的抗甲醇毒蚀能力。相较于不掺氮的Fe/Fe₃C@C-G-2，电催化性能得到了明显的提升。

（2）以氧化石墨烯为催化载体，在液相环境中将其与ZIF-67复合得到催化剂前驱体ZIF-67/GO。并依次通过高温碳化及酸刻工艺得到氮掺杂石墨烯修饰的Co/N共掺杂中空碳纳米胶囊（Co@N-HCCs@NG）。所得到的材料具有以下优点：（i）同时将零维（0D）Co纳米颗粒、零维（0D）空心碳纳米胶囊和二维（2D）石墨烯耦合到同一催化体中，丰富了催化活性物种及界面特性；（ii）中空碳纳米胶囊因其独有的内表面而为整个催化体提供了大的表面积（表面积高达618.12 m²·g^-1）；（iii）杂原子N引入碳骨架可以提高碳基的导电性和电子亲和力，有利于提供更多的活性中心，促进电化学性能的提高。同时，N原子的引入可以促进碳纳米胶囊和氧相关物种的反应性，进而加强各个组分之间的耦合。在碱性条件下的电化学测试表明，Co@N-HCCs@NG展示了高的ORR/OER双功能催化活性。对于ORR，Co@N-HCCs@NG展现了高的ORR初始电位（E_onset=0.98 V）和半波电位（E_1/2=0.86 V）。对于OER，Co@N-HCCs@NG仅仅需要1.528 V的电位就能达到10 mA·cm^-2的电流密度，这也优于商用的RuO₂催化剂（1.583 V）。此外，Co@N-HCCs@NG也表现出优异的催化稳定性。

（3）采用简单的机械配位自组装法成功合成了双氰胺基Co-MOF。以此为金属钴源，将其与氧化石墨烯（GO）进行复合，进而通过高温碳化及酸刻工艺制备得到氮掺杂石墨烯修饰的三维珊瑚礁状碳纳米管组装体（CNAs-NG）纳米材料。在这一策略中，Co-MOF中的双氰胺配体不仅有助于氮的引入，而且可以作为碳纳米管生长的诱导剂。在整个催化剂结构中，金属Co被包裹在碳层中。以氧化石墨烯（GO）为基体对碳纳米管进行桥接，保证碳纳米管的均匀分布。所制备的CNTAs-NG具有三维多孔结构、丰富的缺陷、理想的氮键合类型和高比表面积，这为他们提供了优异的ORR和OER性能。在碱性条件下的电化学测试表明，CNTAs-NG显示了高的ORR初始电位（E_onset=0.97 V）和半波电位（E_1/2=0.85 V）以及低的OER过电位（340 mV@10 mA·cm^-2）。同时，CNTAs-NG也具有比商用贵金属基催化剂（Pt/C，RuO₂）更高的稳定性。

The consumption of fossil fuels has spurred the development of green and renewable energy storage and conversion devices. Zinc-Air Batteries (ZABs) have been targeted as the most promising energy conversion devices due to their environmental-friendliness, high efficiency, long-term operating capacity as well as remarkable energy density. However, the main challenge facing ZABs in widespread application and commercialization is still the bottleneck of low energy conversion efficiency and poor stability caused by sluggish electron transfer dynamics in ORR and OER. Heretofore, it is well known that Pt-based catalysts and RuO₂-based catalysts are the most effective catalysts for ORR and OER, respectively. Unfortunately, their wide application are severely restricted by the high price and terrestrial scarcity. Hence, the design of efficient and low-cost noble-metal-free ORR/OER electrocatalysts is of great significance, which will promote the development of the ZABs. In this paper, a series of transition metal-nitrogen-carbon (M-N-C) nano-catalysts were prepared by means of coordination assembly and in-situ growth using graphene as catalyst carrier and metal-organic framework as metal source. In addition, their catalytic abilities of ORR and OER were investigated. The specific research content is as follows:

Graphene oxide (GO) was selected as a catalytic carrier, the formation of Fe-TA@GO is driven by the coordination assembly between GO, Fe³⁺ and tannic acid (TA) under hydrothermal conditions. Further, a nano-Fe/C catalyst (Fe/Fe₃C@NC-Gs) with a core-shell structure is prepared through a one-step carbonization method using urea with high nitrogen content as the nitrogen source. Fe/Fe₃C@NC-Gs has a unique core-shell structure, abundant mesoporous structure, large surface area and high efficiency nitrogen doping. The close contact between the iron core and the graphite shell is beneficial to adjust the electron density and promote the transfer of electrons from the iron core to the carbon shell. Furthermore, the carbon shell also plays a role of protecting and confining the metal species Fe/Fe₃C, which effectively prevents the alkaline medium from corroding the active species, and also helps to avoid the agglomeration of metal species during the high-temperature carbonization process. The electrochemical test under alkaline conditions shows that Fe/Fe₃C@NC-G-2 has an onset potential of 0.97 V and a half-wave potential of 0.88 V, both of which are higher than those of commercial Pt/C catalysts. In addition, when Fe/Fe₃C@NC-G-2 is used as an ORR catalyst, its stability and methanol resistance are better than commercial Pt/C catalyst. Compared with Fe/Fe₃C@C-G-2, which is not doped with nitrogen, the electrocatalytic performance of Fe/Fe₃C@NC-G-2 has been significantly improved.

The catalyst precursor ZIF-67/GO was synthesized by using graphene oxide as the catalytic carrier in the liquid phase environment. The nitrogen-doped graphene decorated Co/N co-doped hollow carbon nanocapsules (Co@N-HCCs@NG) were prepared by high temperature carbonization and acid etching. The obtained material has the following advantages: (i) Co@N-HCCs@NG simultaneously integrates Co nanoparticles (0D), hollow carbon nanocapsules (0D) and graphene (2D) into a catalytic entity, enriched catalytic active species and interface characteristics; (ii) Hollow carbon nanocapsules provide large surface area (up to 618.12 m²·g^-1) for the whole catalyst due to their unique inner surface; (iii) The introduction of heteroatom N into the carbon skeleton can increase the conductivity and electron affinity of the carbon substrate, thereby generating more active centers to improvethe electrocatalytic performance. Concurrently, the introduction of N atoms can promote the reactivity of carbon nanocapsules and O₂-related species, and strengthen the coupling between the various ingredients. The electrochemical test under alkaline conditions shows that Co@N-HCCs@NG has excellent ORR/OER bifunctional catalytic activity. For ORR, Co@N-HCCs@NG exhibited a high onset potential of 0.98 V and half-wave potential of 0.86 V. For OER, Co@N-HCCs@NG only requires a potential of 1.528 V to reach a current density of 10 mA·cm^-2, which is also better than the commercial RuO₂ catalyst (1.583 V). Moreover, Co@N-HCCs@NG also possessed excellent catalytic stability.

A dicyanamide-based Co-MOF was successfully synthesized by a simple mechanical coordination self-assembly method. It was then compounded with graphene oxide, and finally the nitrogen-doped graphene decorated three-dimensional coral-like carbon nanotube assembly (CNTAs-NG) was prepared by high temperature carbonization and acid etching process. In this tactic, dicyanamide ligand on the Co-MOF not only was instrumental in the introduction of nitrogen but also acted as the inducer of CNTs. In this structure, Co is encapsulated in the carbon layer. Graphene oxide (GO) is chosen as a matrix to bridge the CNTs and ensure the uniform distribution of CNTs. The obtained CNTAs-NG structure possesses 3D open porous texture, abundant defects, desired nitrogen bonding type and high specific surface area, providing them with excellent ORR and OER properties. The electrochemical test under alkaline conditions shows that the optimized CNTAs-NG sample shows a high onset potential (E_onset=0.97 V) and half-wave potential (E_1/2= 0.85 V) for ORR as well as an overpotential of 340 mV at 10 mA·cm^-2 for OER. Simultaneously, CNTAs-NG has higher stability than commercial noble metal-based catalysts (Pt/C, RuO₂).

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