第三主族金属诱导的p-d轨道杂化提升Pd基金属烯在锌空气电池中的氧还原性能

doi:10.1016/S1872-2067(26)64964-9

催化学报

第三主族金属诱导的p-d轨道杂化提升Pd基金属烯在锌空气电池中的氧还原性能

刘文宁^a, 安丽^a,*, 王金明^a, 李如玥^a, 牟洁^a, 龙永德^b, 曲丹^a, 刘弈畅^a, 胡宇翔^b, 汪夏燕^a, 蒋宁^c,*, 孙再成^a,*

^a北京工业大学化学系, 大兴氢能研究院, 北京绿色催化与分离重点实验室, 北京 100124;
^b北京工业大学材料科学与工程学院, 材料低碳循环国家重点实验室, 北京 100124;
^c北京泰丰先行新能源科技有限公司, 北京 102200

收稿日期:2025-09-05 接受日期:2025-09-05
通讯作者: *电子信箱: sunzc@bjut.edu.cn (孙再成), 08131@bjut.edu.cn (安丽), jiangning@pulead.com.cn (蒋宁).
基金资助:
国家自然科学基金(22272003, 22301013, 22579008, 22502012); 国家重点研发计划(2023YFB3810800); 中国博士后科学基金(2023M730140); 北京市教委科研项目(KZ20231000506).

Group IIIA metals-induced p-d orbital hybridization enhances the oxygen reduction performance of Pd based metallene in zinc-air batteries

Wenning Liu^a, Li An^a,*, Jinming Wang^a, Ruyue Li^a, Jie Mu^a, Yongde Long^b, Dan Qu^a, Yichang Liu^a, Yuxiang Hu^b, Xiayan Wang^a, Ning Jiang^c,*, Zaicheng Sun^a,*

^aBeijing Key Laboratory for Green Catalysis and Separation, Department of Chemistry, Institute of Hydrogen Energy Daxing, Beijing University of Technology, Beijing 100124, China;
^bState Key Laboratory of Materials Low-Carbon Recycling, College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124, China;
^cBeijing Taifeng Xianxing New Energy Technology Co., Ltd., Beijing 102200, China

Received:2025-09-05 Accepted:2025-09-05
Contact: *E-mail: sunzc@bjut.edu.cn (Z. Sun), 08131@bjut.edu.cn (L. An), jiangning@pulead.com.cn (N. Jiang).
Supported by:
National Key R&D Program of China (2023YFB3810800), the National Natural Science Foundation of China (22272003, 22301013, 22579008, 22502012), the China Postdoctoral Science Foundation (2023M730140), the R&D Program of Beijing Municipal Education Commission (KZ20231000506), and the Project of Construction of Innovative Teams and Teacher Career Development for Universities and Colleges Under Beijing Municipality (11000024T000003219982).

摘要/Abstract

摘要： 锌空气电池(ZABs)中阴极氧还原反应(ORR)动力学缓慢, 严重限制了其能量转换效率, 因此开发高效且稳定的ORR电催化剂成为关键科学问题. 轨道杂化策略已被广泛应用于调控催化剂的电子结构, 从而加速ORR动力学. 然而, d轨道复杂的几何构型限制了其轨道重叠, 而较窄的能带宽度又导致电子迁移率较低, 从而限制了电子结构的可调范围. 相比之下, p轨道具有更宽的能带和更强的电子离域性, 赋予其更高的电子迁移率与更大的电子结构调控空间. 此外, p轨道近似球对称的特性有利于与d轨道形成有效重叠, 因此, p-d轨道杂化为优化氧中间体吸附能并加速ZABs中的ORR提供了有效策略.
本文将具有相同价电子构型但原子半径、电负性和轨道能级不同的第三主族金属元素(Al, Ga, In)分别引入PdPtMo金属烯中, 以实现p-d轨道杂化. 基于原子半径、电负性和轨道能级的差异, 这些元素在PdPtMo金属烯中将会诱导不同强度的p-d轨道杂化, 从而调控电子结构并优化对中间体的吸附, 提升ORR活性. 在这些主族元素中, Ga由于与Pd/Pt/Mo的原子半径差异最小且轨道能级匹配最优, 可实现最强的p-d轨道杂化. 首先, 通过理论分析验证了设计的合理性. 密度泛函理论计算表明, Ga的原子半径和轨道能量有利于增强p-d轨道杂化, 使PdPtMoGa展现更有利的ORR热力学特性, 同时有效下移d带中心, 削弱对中间体的吸附强度. 随后, 采用湿化学法制备了PdPtMoX金属烯/C (X = Al, Ga, In), 并利用X-射线衍射(XRD)、透射电子显微镜(TEM)、球差校正的高角环形暗场扫描透射电子显微镜、扫描透射电子显微镜-能谱元素分布映射以及原子力显微镜对其结构进行了系统表征. 通过X射线光电子能谱(XPS)对不同p-d轨道杂化带来的电子结构的影响进行了探究; 结果显示, Ga的引入增强了p-d轨道杂化, 显著促进体系内的电子转移并进一步下移d带中心, 从而优化了对含氧中间体的吸附. X-射线吸收谱和原位傅里叶变换红外光谱分析表明, Ga与Pd配位诱导的强p-d轨道杂化能够更有效地加速O₂质子化生成OOH*, 并迅速解离为O*, 实现优异的ORR性能及锌空气电池活性. 最后, 对材料的催化活性和稳定性进行评估, PdPtMoGa金属烯/C催化剂在0.9 V (相对于可逆氢电极, vs. RHE)下的质量活性高达6.07 A mg^-1_Pt, 半波电位为0.94 V (vs. RHE), 性能优于商业Pt/C, PdPtMo, PdPtMoAl和PdPtMoIn金属烯/C催化剂. 值得注意的是, PdPtMoGa金属烯/C在30,000次循环后仍能保持优异性能, 结合稳定后催化剂的XPS, XRD和TEM表征进一步确认了结构稳定性. 此外, 在实际锌空气电池中, PdPtMoGa金属烯/C实现了207.2 mW cm^-2的峰值功率密度, 并可稳定运行超过180 h.
综上, 本研究系统研究了不同第三主族元素引起的p-d轨道杂化强度差异对ORR和ZAB性能的影响, 强调了轨道杂化工程在优化催化性能中的关键作用, 并展示了其在下一代能源应用中的巨大潜力.

关键词: p-d轨道杂化, 第三主族金属元素, Pd基金属烯, 电子结构, 氧还原反应, 锌空气电池

Abstract: p-d orbital hybridization offers a powerful strategy to optimize oxygen adsorption energies and accelerate the oxygen reduction reaction (ORR) in zinc-air batteries (ZABs). Here, we introduce Group IIIA elements (Al, Ga, In) into PdPtMo metallenes to systematically tune p-d orbital interactions. Among them, Ga exhibits the smallest atomic radius mismatch and optimal orbital energy alignment, and the enhanced p-d orbital hybridization in PdPtMoGa metallenes promotes electron transfer. The PdPtMoGa metallene/C catalyst achieves an exceptionally high mass activity of 6.07 A mg^-1_Pt at 0.9 V vs. RHE and a half-wave potential of 0.94 V, surpassing commercial Pt/C. Density functional theory calculations, X-ray absorption spectroscopy, in-situ Fourier-transform infrared spectroscopy, and other characterizations reveal that the strong p-d orbital hybridization induced by Ga coordination with Pd in PdPtMoGa metallenes lowers the d-band center and weakens the adsorption of oxygen intermediates. Remarkably, the catalyst retains stability over 30,000 cycles. When deployed in ZABs, PdPtMoGa metallene/C achieves a peak power density of 207.2 mW cm^-2 and stable operation exceeding 180 h. Overall, this study presents a rational design strategy for high-activity and durable Pd-based electrocatalysts and elucidates the specific roles of Group IIIA elements in modulating p-d orbital hybridization.

Key words: p-d orbital hybridization, Group IIIA elements, Pd-based metallenes, Electronic structure, Oxygen reduction reaction, Zinc-air batteries

刘文宁, 安丽, 王金明, 李如玥, 牟洁, 龙永德, 曲丹, 刘弈畅, 胡宇翔, 汪夏燕, 蒋宁, 孙再成. 第三主族金属诱导的p-d轨道杂化提升Pd基金属烯在锌空气电池中的氧还原性能[J]. 催化学报, DOI: 10.1016/S1872-2067(26)64964-9.

Wenning Liu, Li An, Jinming Wang, Ruyue Li, Jie Mu, Yongde Long, Dan Qu, Yichang Liu, Yuxiang Hu, Xiayan Wang, Ning Jiang, Zaicheng Sun. Group IIIA metals-induced p-d orbital hybridization enhances the oxygen reduction performance of Pd based metallene in zinc-air batteries[J]. Chinese Journal of Catalysis, DOI: 10.1016/S1872-2067(26)64964-9.

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