石墨烯纳米片锚定Pt-N3O强配位结构加速电催化氧还原四电子转移过程

doi:10.1016/S1872-2067(25)64768-1

催化学报 ›› 2025, Vol. 77: 227-235.DOI: 10.1016/S1872-2067(25)64768-1

石墨烯纳米片锚定Pt-N₃O强配位结构加速电催化氧还原四电子转移过程

王心琪^a^,¹, 张雪元^a^,¹, 焦梦改^a^,^c^,¹, 马润林^a, 谢芳^a, 万浩^a, 沈祥建^a, 张利利^a^,^*(), 马炜^a^,^b^,^*(), 周震^a^,^d^,^*()

^a郑州大学化学化工学院, 新能源科学与工程交叉研究中心(IRC4SE²), 河南郑州 450001
^b中南大学粉末冶金国家重点实验室, 湖南长沙 410083
^c南开大学先进能源材料化学教育部重点实验室, 天津 300071
^d南开大学材料科学与工程学院, 新能源材料化学研究所, 新能源转化与存储交叉科学中心, 天津 300350

收稿日期:2025-04-28 接受日期:2025-06-11 出版日期:2025-10-18 发布日期:2025-10-05
通讯作者: *电子信箱: llzhang@zzu.edu.cn (张利利),mawei@zzu.edu.cn (马炜),zhenzhou@zzu.edu.cn (周震).
作者简介:¹共同第一作者.
基金资助:
国家自然科学基金(22208322);河南省自然科学基金(242300421230);粉末冶金国家重点实验室基金(Sklpm-KF-021);河南省高等学校重点科研项目(24A530009);郑州大学青年教师专项基金(JC23257011)

The strong Pt-N₃O coordination in graphene nanosheets accelerates the 4e⁻ electrocatalytic oxygen reduction process

Xinqi Wang^a^,¹, Xueyuan Zhang^a^,¹, Menggai Jiao^a^,^c^,¹, Runlin Ma^a, Fang Xie^a, Hao Wan^a, Xiangjian Shen^a, Li-Li Zhang^a^,^*(), Wei Ma^a^,^b^,^*(), Zhen Zhou^a^,^d^,^*()

^aInterdisciplinary Research Center for Sustainable Energy Science and Engineering (IRC4SE²), School of Chemical Engineering, Zhengzhou University, Zhengzhou 450001, Henan, China
^bState Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, Hunan, China
^cKey Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071, China
^dSchool of Materials Science and Engineering, Institute of New Energy Material Chemistry, Renewable Energy Conversion and Storage Center, Nankai University, Tianjin 300350, China

Received:2025-04-28 Accepted:2025-06-11 Online:2025-10-18 Published:2025-10-05
Contact: *E-mail: llzhang@zzu.edu.cn (L.-L. Zhang), mawei@zzu.edu.cn (W. Ma), zhenzhou@zzu.edu.cn (Z. Zhou).
About author:¹Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22208322);Natural Science Foundation of Henan(242300421230);State Key Laboratory of Powder Metallurgy(Sklpm-KF-021);Key Research Projects of Higher Education Institutions of Henan Province(24A530009);Special Fund for Young Teachers from the Zhengzhou University(JC23257011)

摘要/Abstract

摘要：

电化学技术驱动的可持续能源转化与利用, 因其高效、清洁的特点, 正逐步成为替代传统化石能源的主流选择, 并受到广泛关注. 燃料电池和金属-空气电池作为清洁高效的能源转化与储能技术, 在长续航动力电池和高能量密度储能领域展现出卓越的应用潜力, 近年来发展迅猛. 阴极氧还原反应(ORR)作为能量转换的核心环节, 直接决定了电催化过程的整体反应效率. 然而, ORR过程涉及多步电子耦合质子转移以及多种反应中间体的生成与转化, 导致其反应动力学缓慢且反应能垒较高. 虽然Pt基催化剂在ORR过程中表现出优良的性能和良好的实用性, 但由于其储量低、价格高, 严重制约了大规模推广应用. 因此, 开发高效低Pt含量ORR电催化剂, 已成为当前研究的迫切需求.

近年来, 金属-氮-碳(M-N-C)单原子催化剂因其极高的原子利用率、可调控的电子结构以及较高的能量转换效率而备受关注. 金属有机框架衍生的碳基材料, 凭借其高比表面积以及均匀的金属分散性, 为制备M-N-C单原子催化剂提供了理想的载体. 因此, 本文创新性地提出了一种无机盐介导的二次煅烧策略, 通过KCl和LiCl辅助剥离Zn-ZIF, 获得了超薄的氮/氧掺杂石墨烯纳米片(N/O-GNs), 为高暴露的Pt-N₃O活性结构提供了稳定的锚定位点, 成功构筑了氮、氧共掺杂石墨烯纳米片负载的Pt单原子催化剂(Pt-N/O-GNs), 该Pt-N/O-GNs催化剂中Pt含量约为0.44 wt%. 并且, 通过引入N和O杂原子, 形成不对称Pt-N₃O结构, 实现了对金属活性位的表面配位环境调控, 进而有效加速氧还原四电子转移过程(氧还原起始电位和半波电位分别为0.99和0.88 V), 催化剂稳定性和抗毒化能力得到同步提升. 理论计算研究也证实了少层石墨烯中掺杂的异质原子对Pt单原子的稳定锚定作用, 以及氧还原反应中的四电子转移过程是更受热力学支持的反应途径. 此外, 以Pt-N/O-GNs作为阴极催化剂组装应用于锌-空气电池, 展现出优异的功率密度和循环稳定性.

综上所述, 本研究利用无机盐剥离工艺成功实现了高暴露Pt单原子在超薄石墨烯载体上的稳定锚定, 显著提升了低Pt材料的电催化性能. 实验与理论研究均表明, 该催化剂的优异催化性能主要归因于Pt-N₃O配位结构在氧还原反应过程中兼顾了高活性与高稳定性. 这些发现为单金属位点电催化剂的定向设计与精准制备提供了新的理论和实践依据, 同时也为单原子催化剂的高效合成开辟了具有普适性的新路径.

关键词: 氧还原反应, Pt-N₃O活性中心, Pt单原子, 超薄碳层, 金属-载体相互作用

Abstract:

Single-metal sites anchored in nitrogen-doped nanocarbons are recognized as potent electrocatalysts for applications in energy conversion and storage. Here, an innovative inorganic salt-mediated secondary calcination strategy was developed to construct robust Pt single-atom catalysts on nitrogen- and oxygen-doped graphene nanosheets (Pt-N/O-GNs), thereby significantly enhancing the efficiency of the electrocatalytic oxygen reduction reaction (ORR). The ultrathin N/O-GNs, obtained by stripping Zn-ZIF with auxiliaries of KCl and LiCl, provide stable anchoring sites for highly exposed Pt-N₃O active structures. The Pt-N/O-GNs catalyst, featuring a low Pt loading of 0.44 wt%, demonstrates exceptional mass activity in the ORR process. It attains an impressive onset potential of 0.99 V and a half-wave potential of 0.88 V. The zinc-air battery driven by the Pt-N/O-GNs displays superior power density and cycle stability. Theoretical computational studies reveal that the structure of heteroatoms doped in few-layer graphene facilitates the stable anchoring of single-atom configurations. The findings provide new perspectives for the tailored design and fabrication of single-metal-site electrocatalysts.

Key words: Oxygen reduction reaction, Pt-N₃O active center, Pt single atom, Ultra-thin carbon layer, Metal-support interaction

王心琪, 张雪元, 焦梦改, 马润林, 谢芳, 万浩, 沈祥建, 张利利, 马炜, 周震. 石墨烯纳米片锚定Pt-N₃O强配位结构加速电催化氧还原四电子转移过程[J]. 催化学报, 2025, 77: 227-235.

Xinqi Wang, Xueyuan Zhang, Menggai Jiao, Runlin Ma, Fang Xie, Hao Wan, Xiangjian Shen, Li-Li Zhang, Wei Ma, Zhen Zhou. The strong Pt-N₃O coordination in graphene nanosheets accelerates the 4e⁻ electrocatalytic oxygen reduction process[J]. Chinese Journal of Catalysis, 2025, 77: 227-235.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64768-1

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图/表 5

Fig. 1. (a) Schematic representation of the synthesis processes for Pt-N/O-GNs derived from Zn-ZIF. HR-TEM images (b), AC-STEM image (c), and HAADF-STEM image and EDS elements mapping (d) of Pt, C, N in Pt-N/O-GNs.

Fig. 2. XPS curves of N 1s (a), O 1s (b), and Pt 4f (c) orbitals for prepared Pt-based samples. Pt L3-edge XANES spectra (d) and The k2-weighted FT-EXAFS spectra (e) of Pt-N/O-GNs, Pt, and PtO2, respectively. (f) Corresponding XAFS spectrum fitting curve in k2 space for Pt in Pt-N/O-GNs. WT of Pt in Pt foil (g), PtO2 (h), and Pt-N/O-GNs (i).

Fig. 3. Electrocatalytic ORR performance tests of catalysts. (a) LSV curves. (b) ORR activities comparison. (c) Tafel slopes. (d) Cdl values. (e) LSV curves obtained at various rotating rates in 0.1 mol L-1 KOH, and the fitted K-L plots and the calculated electron transfer number (n) in the inserted graph. (f) n value and HO2?% for Pt-N/O-GNs evaluated by RRDE methods.

Fig. 4. Electrocatalytic stability and Zn-air battery performance tests. (a) LSV curves of Pt-N/O-GNs at 1600 rpm at 5 mV s?1 before and after 5000 CV cycles for ORR in 0.1 mol L?1 KOH. (b) Chronopotentiometry measurements on Pt/C and Pt-N/O-GNs electrodes. (c) LSV curves of Pt-N/O-GNs and Pt/C in O2-saturated 0.1 mol L?1 KOH and mixed electrolyte by adding 0.5 mol L?1 CH3OH. (d) CV curves of Pt/C and Pt-N/O-GNs in N2-saturated 0.1 mol L?1 KOH + 0.5 mol L?1 CH3OH (i), and chronoamperometric response of Pt-N/O-GNs at 0.75 V under 1600 rpm after adding methanol at 200 s in O2-saturated 0.1 mol L?1 KOH (ii). (e) Charge/discharge polarization and power density curves of the ZAB based on Pt-N/O-GNs and Pt/C catalysts, respectively. (f) Galvanostatic discharge-charge cycle curves of the ZAB with Pt-N/O-GNs electrode at 10 mA cm?2.

Fig. 5. Mechanism analysis of catalysts. Schematic diagram (a) and free energy comparison (b) of the possible 2e? or 4e? ORR pathway on the Pt-N3O center in monolayer carbon. (c) The configurations of different adsorption products of Pt binding on monolayer carbon substrates.

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石墨烯纳米片锚定Pt-N₃O强配位结构加速电催化氧还原四电子转移过程

The strong Pt-N₃O coordination in graphene nanosheets accelerates the 4e⁻ electrocatalytic oxygen reduction process

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