石墨炔/石墨烯基催化剂催化氮气/氧气还原的研究

  电催化氮气还原（NRR）和氧气还原（ORR）可以将N₂和O₂分别转换为NH₃和新能源，对人类的生存和可持续发展具有重要的意义。当前，工业上的合成氨技术是采用成熟的Haber-Bosch工艺，而该技术需要在高温（300-500 ^oC）和高压（> 200 atm）条件下才能进行，使得整个过程的年能耗占世界年能耗的2%，同时还伴随着每年近400兆吨的CO₂排放。室温条件下的NRR技术相比能耗严重的Haber-Bosch合成氨工艺具有得天独厚的优势，但其目前的合成氨效率仍然无法满足实际应用的需求。此外，ORR中所使用的昂贵的铂基贵金属催化剂使新能源技术的开发成本一直高居不下，导致至今未能投入大规模应用中。基于此，合理设计开发高效廉价的NRR/ORR催化剂及对电解体系进一步的优化，不仅可以提高合成氨效率还可以降低新能源技术成本。本论文针对NRR效率的提高从催化剂调控和电解体系优化两方面入手构筑了新型石墨双炔（GDY）基NRR催化剂并开发了高压电解装置，有效促进了NRR的合成氨效率及其潜在的实际应用奠定了基础。此外，本文采取协同催化策略制备了过渡金属和多孔碳基复合的廉价高效ORR催化剂，对高活性非贵金属催化剂的开发提供新的思路。研究内容主要包括以下几个方面：

  开发Cl₂刻蚀策略对GDY进行减薄和掺杂，构筑出Cl掺杂的超薄GDY纳米片（Cl-GDY）。形貌表征显示了所制备的Cl-GDY纳米片仅有2 nm的厚度，而且结构分析证明了Cl元素的成功掺杂并在GDY基底上形成更多的缺陷并调控了材料的电子云密度。NRR实验表明，Cl-GDY催化剂在-0.45 V和-0.4 V相对可逆氢电极的电压下呈现出最佳的合成氨产率10.7 g h^-1cm^-2和最高的法拉第效率8.7%，该性能相比于纯GDY提高了近4倍。理论计算显示了Cl-GDY相比于纯GDY更有利于NRR过程，其对应的电势限制步骤的能量降低了0.11 eV。

  催化活性中心的π电子反馈能力可以促进NRR缓慢的动力学过程。通过原位配位的方法合成一系列GDY负载的低价态金属单原子催化剂M SA/GDY（M = Cr、Mo、W、Mn、Re），从而对催化中心的π电子反馈能力进行优化。球差电镜和同步辐射表征证明了所制备的M SA/GDY具有单原子分散的低价态的M-C₄金属中心。严谨的NRR实验表明所制备的M SA/GDY催化剂的氮还原性能从高所到低为：Re SA/GDY > Mo SA/GDY > Cr SA/GDY > W SA/GDY >> Mn SA/GDY（其中，Mn SA/GDY基本上没有氮还原催化性能）。值得注意的是，Re SA/GDY样品在-0.35 V相对可逆氢电极电压下呈现出其最佳的合成氨产率15.3 μg h^-1 cm^-2和法拉第效率8.07%，该性能进一步得到了同位素实验的证实。理论计算证明由于Re SA/GDY强的π电子反馈能力，使得*N₂还原加氢到*NNH的能量需求仅为+0.42 eV，而这一步骤被认为是NRR的决速步骤。机理分析还揭示了Re SA/GDY催化剂上呈现一种新的NH₃解离机制，其中N₂或H₂O可以在Re单原子上与NH₃的进行共同吸附有效促进产物NH₃的脱附，从而降低了NRR的远端和混合反应路径的能量输入。

  通过单原子催化剂与高压电解反应釜的协同作用，同时调节NRR的动力学和热力学驱动力。NRR催化剂的构筑是通过简单的一步法合成的GDY负载的单原子催化剂M SA/GDY（M = Rh、Ru、Co），金属中心的配位结构为M-C₄。在高的N₂压力下，N₂的溶解度升高，更多的N₂分子可以传输到单原子催化剂的表面，从而提高了NRR的效率并且抑制了析氢副反应。在55 atm的N₂压力下，Rh SA/GDY催化剂在-0.2 V下呈现出74.15 μg h^-1 cm^-2的合成氨产率、20.36%的法拉第效率以及0.35 mA的合成氨电流，该性能分别是常压条件下的7.3、4.9和9.2倍。通过充分纯化后的¹⁵N₂同位素实验证明了实验中所得到的NH₃确实来自于N₂的还原。同样，所制备的Ru SA/GDY和Co SA/GDY催化剂在高压电催化体系中也呈现出较好的氮还原性能，表明提高N₂的压力对催化剂的氮还原性能提高具有普适性。理论计算证明了高压条件下有利于N₂在单原子催化剂上的吸附同时还降低NRR能垒。

  将无定型CoN_x均匀负载在三维多孔氮掺杂石墨烯气凝胶NGA上，所制备的CoN_x/NGA复合物可以同时结合CoN_x高催化活性和NGA的优异导电性的特点。此外，NGA基底的分等级多孔特性可以促进催化剂的传质和电子转移过程。基于此，所制备的CoN_x/NGA在ORR中呈现出的起始电位为0.93 V，半波电位为0.83 V，极限电流密度为5.4 mA cm^-2，该性能与贵金属铂催化剂相当。在锌空电池中，CoN_x/NGA呈现出638 Wh kg^-1的质量能量密度，表现出潜在的应用价值。

Electrocatalytic N₂ reduction reaction (NRR) and O₂ reduction reaction (ORR) offer a green path for N₂ to NH₃ and O₂ to new energy conversions, both of which are of great significance for human thrive and development. The present-day industrial ammonia is synthesized by a mature technology of the Harber-Bosch process, which requires harsh conditions of high temperature (300-500 ℃) and high pressure (> 200 atm). However, more than 2% of the global energy supply was inputted to the synthesis of ammonia, along with gigatons of annual CO₂ emissions. Unlike the energy-intensive Haber-Bosch process, ammonia synthesis under ambient conditions over NRR shows many advantages, while its efficiency achieved by far is still too low to meet the practical command. On the other hand, the large-scale application of the new energy technology is hampered by the expensive noble Pt catalysts utilization on ORR. In this scenario, rational engineering of efficient but cost-effective catalysts with further optimizing the electrocatalytic systems play key roles in promoting the NRR efficiency and reducing the cost of new energy technology. In this thesis, we constructed graphdiyne (GDY) based electrocatalysts and developed a pressurized electrocatalytic system to boost the electrochemical ammonia production efficiency. In addition, the synergies between transition metal catalysts with porous graphene lever a superior ORR performance, which would pave an avenue for effective and no-precious ORR catalysts design. The following results are achieved:

  A novel Cl doped ultrathin GDY nanosheets (Cl-GDY) was nanostructured by Cl₂ corrosion strategy, the process of which not only introduced a heteroatom of Cl dopant in the host but also etched the pristine GDY into ultrathin nanosheets. Morphology characterization showcased the ultrathin nature of as-prepared Cl-GDY with a thickness of ~2 nm. Moreover, structural analysis verified the success of Cl doping on GDY, leading to more defect formation and electron density modulation. Detailed electrochemical NRR experiments confirmed that the Cl-GDY catalyst affords a fairly high NH₃ yield rate of 10.7 g h^-1 cm^-2 and Faradic efficiency of 8.7% at -0.45 V and -0.4 V versus reversible hydrogen electrode (RHE), respectively, which shows 4-fold enhancement than that of pristine GDY. Furthermore, density functional theory revealed that Cl doping is beneficial for N₂ reduction on the GDY host by lowing the limiting potential by 0.11 eV to the pristine GDY.

  The π-backdonation ability of catalytic centers is vital to facilitating the sluggish kinetics of NRR. We put forward a versatile in-situ coordination approach to the synthesis of a series of single atoms anchored on GDY backbones (denoted as M SA/GDY, M=W, Mo, Re, Mn) to optimize the π-backdonation ability of metal centers. The microscopy and synchrotron-based X-ray absorption spectroscopy verify the atomically dispersed M-C₄ moieties with a low metal valence state were well-established in the as-prepared M SA/GDY catalysts. Under rigorous ENRR protocol, an activity trend of Re SA/GDY > Mo SA/GDY > Cr SA/GDY > W SA/GDY >> Mn SA/GDY (no activity) was delivered. Remarkably, the Re SA/GDY displayed an optimal NH₃ yield rate of 15.3 μg h^-1 cm^-2 with a Faradic efficiency of 8.07% at -0.35 V versus reversible hydrogen electrode, which is also quantitatively confirmed by the isotope ¹⁵N₂ measurements. Furthermore, theoretical studies revealed that the strong M-to-N₂ π-backdonation of Re SA/GDY renders a low energy requirement of +0.42 eV for the reductive hydrogenation of *N₂ to *NNH, which is considered as the bottleneck of NRR. And a novel NH₃ desorption mechanism through N₂ co-adsorption on a Re-NH₃ intermediate is proposed to facilitate the NH₃ desorption from Re SA/GDY with a low energy input of +0.82 eV for the distal and mix pathways.

  By positive cooperation of metal single-atom catalysts with a pressurized reaction system, the chemical kinetics and thermodynamic driving forces of the NRR were regulated. The applied catalysts were the densely populated single metal atoms on GDY (M SA/GDY, M = Rh, Ru and Co) by using a mild and one-pot approach, which features M-C₄ coordination. Under high N₂ partial pressure, the dissolved N₂ concentration in water increases and more N₂ could be delivered to the electrode surface, leading to the amplified NRR activity with a simultaneously retarded hydrogen reduction reaction. As a result, a fairly high ammonia yield rate of 74.15 μg h^-1 cm^-2, a Faradic efficiency of 20.36% and an NH₃ partial current density of 0.35 mA cm^-2 were achieved for Rh SA/GDY at 55 atm of N₂, which shows 7.3-folds, 4.9-folds and 9.2-folds enhancement in comparison with those obtained in ambient conditions. The isotope experiment using adequately cleaned ¹⁵N₂ further ensured the ammonia electrosynthesis from N₂. Additionally, similar NRR activity promotion was observed on the as-prepared Ru SA/GDY and Co SA/GDY under the pressurized electrolysis systems, demonstrating a general and cooperative strategy of elevating N₂ partial pressure in reprogramming NRR. Theoretical calculations reveal that the N₂ adsorption and kinetic activity for Rh SA/GDY are enhanced under the pressurized conditions, facilitating the ENRR process.

  Integration of amorphous CoN_x with 3D porous nitrogen-doped graphene aerogel (NGA) forming the CoN_x/NGA hybrid inherits both prominent catalytic activity of CoN_x and excellent conductivity of NGA. Moreover, the hierarchical pores over the NGA substrate dramatically promote the catalyst's mass and electron transfer process. As a result, the CoN_x/NGA exhibited an onset potential of 0.93 V, a half-wave potential of 0.83 V and a limited current density of 5.4 mA cm^-2, which is comparable to the noble Pt/C catalysts. Furthermore, the CoN_x/NGA drives a high mass-energy density of 638 wh kg^-1 in a Zn-air battery, signifying its potential practical applications.

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