RuOx-PtZn催化剂加速水活化过程实现高效的直接甲醇燃料电池

doi:10.1016/S1872-2067(25)64836-4

催化学报 ›› 2026, Vol. 80: 304-315.DOI: 10.1016/S1872-2067(25)64836-4

RuO_x-PtZn催化剂加速水活化过程实现高效的直接甲醇燃料电池

梁宸嘉^a^,¹, 姚均^a^,¹, 高宁泽^a^,¹, 侯晓霞^a, 卢皓玉^a, 赵锐瑶^a, 庄子恒^a, 杨杰^a, 王丽雯^a, 郭向可^a, 薛念华^a, 王涛^b, 祝艳^a, 丁维平^a^,^*()

^a南京大学化学化工学院, 介观化学重点实验室, 江苏南京 210023
^b江苏介观催化材料科技有限公司, 江苏苏州 215634

收稿日期:2025-06-15 接受日期:2025-08-08 出版日期:2026-01-18 发布日期:2026-01-05
通讯作者: 丁维平
作者简介:第一联系人：¹共同第一作者
基金资助:
国家自然科学基金(91963206);国家自然科学基金(21932004);国家科技部(2021YFA1500301)

RuO_x-PtZn catalyst boosting methanol electro-oxidation by synergic water-activation for high-performance direct methanol fuel cell

Chenjia Liang^a^,¹, Jun Yao^a^,¹, Ningze Gao^a^,¹, Xiaoxia Hou^a, Haoyu Lu^a, Ruiyao Zhao^a, Ziheng Zhuang^a, Jie Yang^a, Liwen Wang^a, Xiangke Guo^a, Nianhua Xue^a, Tao Wang^b, Yan Zhu^a, Weiping Ding^a^,^*()

^aKey Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, Jiangsu, China
^bJiangsu Meso Catalytic Materials Technology Co., Ltd, Suzhou 215634, Jiangsu, China

Received:2025-06-15 Accepted:2025-08-08 Online:2026-01-18 Published:2026-01-05
Contact: Weiping Ding
About author:First author contact:¹These authors contributed equally.
Supported by:
National Natural Science Foundation of China(91963206);National Natural Science Foundation of China(21932004);Ministry of Science and Technology of China(2021YFA1500301)

摘要/Abstract

摘要：

直接甲醇燃料电池(DMFC)是一种先进的可持续能源转换技术, 其燃料甲醇的能量密度高达6.13 kW h kg^‒1且与我国现有的燃料基础设施具有较强的兼容性. 然而, DMFC实际应用仍受限于两大关键瓶颈:缓慢的甲醇氧化反应(MOR)动力学和较差的稳定性. 这迫使当前体系需使用高载量(>2 mg cm^‒2)且昂贵的PtRu基催化剂, 却仅能提供不足80 mW cm^‒2的功率密度, 严重制约了DMFC的商业化落地应用.

为实现质子交换膜型DMFC的高功率和低铂化目标, 本研究在铂锌纳米颗粒表面构建原子级分散的氧化态钌(RuO_x)物种作为高效水活化中心, 以协同促进MOR过程. 通过锌的电子调控作用, 钌物种趋于稳定的+2价态, 显著增强了界面水分子的捕获与解离能力, 并促进吸附态的羟基自由基(*OH)向相邻铂位点的迁移, 从而实现了相邻铂位点上一氧化碳吸附物的快速脱除. RuO_x-PtZn催化剂在三电极测试体系中展现出卓越的MOR质量活性, 达到2.71 A mgPt^‒1, 较商业Pt/C提升3.7倍; 将其作为阳极催化剂组装的DMFC实现了191.2 mW cm^‒2的峰值功率密度, 同时保持了125 h的稳定性. 为深入理解其高性能机制, 本文结合第一性原理分子动力学模拟和电化学原位傅里叶变换红外光谱, 发现钌中心周围形成了以氧端朝下(O-down)方式排列的致密水分子网络. 该结构有效促进了界面水捕获, 并经由关键中间体RuO(OH)₂的形成显著降低水解离能垒. 动力学同位素效应测试(CH₃OH/H₂O vs. CH₃OH/D₂O)显示, 在0.85 V vs. RHE电位下, RuO_x-PtZn/C催化剂的J_H2O/D2O比值为4.2, 而RuO_x-Pt/C的比值高达16.2, 这直接证实了RuO_x-PtZn/C具有卓越的水活化效率, 与密度泛函理论计算水活化过渡态的结果一致. 差分电化学原位质谱结果表明, 该催化剂在较低过电位下即可完成6电子转移过程, 显著提升了甲醇完全电氧化的反应动力学.

综上, 本研究通过实验与理论相结合的方法, 系统阐释了RuO_x-PtZn/C催化剂在甲醇电氧化反应中的协同促进机制, 不仅为设计高效稳定的MOR催化剂提供了新思路, 也为推动DMFC的实际应用奠定了理论与技术基础.关键词: 氧化态钌物种; RuO(OH)₂结构; 水活化; 甲醇氧化反应; 直接甲醇燃料电池

Abstract:

For achieving high-power and low-platinum direct methanol fuel cell (DMFC) under proton-exchange-membrane, we introduce the oxidation-state ruthenium species as H₂O-activation centers stabilized on PtZn NPs to boost methanol-oxidation reaction (MOR). The Zn-regulated Ru centers, approaching bivalent states, enhance interfacial H₂O-capture/dissociation and OH-transfer, enabling rapid CO* removal from adjacent Pt sites. It exhibits an outstanding mass activity of MOR at 2.71 A mg_Pt^-1 and powers a DMFC with 191.2 mW cm^-2 peak density (382.4 W g_Pt^-1) while maintaining 125-hour stability, higher than documented results to date, essentially different from traditional alloy catalysts. Combined ab initio molecular dynamics simulations and in-situ spectroscopy reveal a dense O-down water network around Ru centers, where intermediate RuO(OH)₂ structure significantly deceases the H₂O-dissociation barrier. Kinetic isotope effect tests (CH₃OH/H₂O vs. D₂O) show J_H2O/D2O = 4.2 for RuO_x-PtZn/C at 0.85 V_RHE, versus 16.2 for RuO_x-Pt/C, directly confirming superior water activation efficiency of RuO_x-PtZn/C. We envision that the comprehensive understanding of high-performance MOR on RuO_x-PtZn/C through experimental-theoretical approaches will contribute to the practical application of DMFC as early as possible.

Key words: Oxidation-state ruthenium, RuO(OH)₂, H₂O activation, Methanol oxidation reaction, Direct methanol fuel cell

梁宸嘉, 姚均, 高宁泽, 侯晓霞, 卢皓玉, 赵锐瑶, 庄子恒, 杨杰, 王丽雯, 郭向可, 薛念华, 王涛, 祝艳, 丁维平. RuO_x-PtZn催化剂加速水活化过程实现高效的直接甲醇燃料电池[J]. 催化学报, 2026, 80: 304-315.

Chenjia Liang, Jun Yao, Ningze Gao, Xiaoxia Hou, Haoyu Lu, Ruiyao Zhao, Ziheng Zhuang, Jie Yang, Liwen Wang, Xiangke Guo, Nianhua Xue, Tao Wang, Yan Zhu, Weiping Ding. RuO_x-PtZn catalyst boosting methanol electro-oxidation by synergic water-activation for high-performance direct methanol fuel cell[J]. Chinese Journal of Catalysis, 2026, 80: 304-315.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64836-4

https://www.cjcatal.com/CN/Y2026/V80/I1/304

图/表 8

Scheme 1. Schematic diagram to elucidate the preparation of RuOx-PtZn catalyst and its synergic mechanism for MOR with bivalent Ru.

Fig. 1. The Structural Characterization of RuOx-PtZn/C. (A) Schematic diagram of catalytic-deposition process of Ru on PtZn NPs surface. (B) The HR-TEM image of RuOx-PtZn/C. Inset shows the size distribution of RuOx-PtZn NPs. (C) The HADDF-STEM image of RuOx-PtZn NPs. (D) The intensity surface plot of enlarged region in Fig. 1(C). (E) The EDS mapping of RuOx-PtZn NPs, including Pt, Zn, and Ru element and mixing.

Fig. 2. The electronic and coordinated structure of RuOx-PtZn/C. The Ru K-edge XANES and charge-state fitting (A), fitting EXAFS (B) and Wavelet transforms for the k2-weighted Ru K-edge EXAFS signal (C) for RuOx-Pt/C and RuOx-PtZn/C. The XPS Pt 4f (D) and Zn 2p3/2 (E) spectra of PtZn/C and RuOx-PtZn/C (Inset: the schematic diagram of electron transfer between Ru and Zn).

Fig. 3. The MOR evaluation of RuOx-PtZn/C in half cell and DMFC. (A) The CV curves of different catalysts in N2-saturated 0.1 mol L?1 HClO4 and 1.0 mol L?1 MeOH. (B) The mass activity (MA) improvement after Ru deposition on Pt/C and PtZn/C. (C) The overpotential (@10 mA cm?2) and MA of different elements on PtZn surface. (D) The comparison of MOR activity between RuOx-PtZn/C and reported catalysts in a three-electrode system [3,5,7,8,17,19,20,35-39]. (E) The polarization and power curve in DMFC at 90 °C with iR-free (high-purity O2 with 100% RH: 500 sccm; 2.0 mol L?1 MeOH: 2 mL min?1). (F) The comparison of RuOx-PtZn/C and reported catalysts as anodes for DMFC [5-8,17,39-41]. (G) The stability test of RuOx-PtZn/C on the 2×2 cm MEA at 70 °C without iR-correct (high-purity and atmospheric-pressure O2 with 67% RH: 300 mL min?1; 1.0 mol L?1 MeOH: 0.5 mL min?1).

Fig. 4. The surface species evolution on RuOx-PtZn/C during MOR process. (A) Electrochemical in-situ FTIR spectra for PtZn/C, RuOx-Pt/C and RuOx-PtZn/C in N2-saturated 0.1 mol L?1 HClO4 and 1.0 mol L?1 MeOH electrolyte. (B) The peak fitting of O-H stretching vibration at 0.6 V from the electrochemical in-situ FTIR spectra for PtZn/C, RuOx-Pt/C and RuOx-PtZn/C. (C) The KIE test of RuOx-Pt/C and RuOx-PtZn/C in N2-saturated 0.1 mol L?1 HClO4 and 1.0 mol L?1 MeOH electrolyte with H2O or D2O as medium. (D) The m/z = 44 signal in DEMS of RuOx-Pt/C and RuOx-PtZn/C in N2-saturated 0.1 mol L?1 HClO4 and 1.0 mol L?1 MeOH electrolyte. (E) The schematic diagram of enhancing H2O-activation process, including H2O-capture and H2O-dissociation, on RuOx-PtZn/C.

Fig. 5. The properties of multi-layer water around RuOx-PtZn. (A) The interface model between different catalysts and methanol aqueous solution. (B) The comparison of H2O molecules, H-bond number, and average H-band bond length within the range of 6 ? above the catalyst surface. (C) The radial distribution function of Ru-O (O atom in H2O) for RuOx-Pt and RuOx-PtZn. (D) The statistics of z-axis distribution of H2O molecules on different catalyst surfaces.

Fig. 6. Full elucidation about the MOR mechanism on RuOx-PtZn/C. (A) The various intermediate models during the MOR process on the RuOx-Pt3Zn (111) surface. (B) The Gibbs free energy diagram for H2O# activation and CO* oxidation process. (C) The pCOHP of Ru-O in RuOx-Pt (111) and RuOx-Pt3Zn (111), with H2O# adsorption. (D) The transition state of H2O + # + *→ H* + OH# process.

Table 1 The key process energy barrier and key species adsorption energy.

	H₂O-dissociation barrier (eV)	OH^#-adsorption energy (eV)	CO*-oxidation barrier (eV)
Pt₃Zn	0.860	‒0.791	1.487
RuO_x-Pt	0.492	‒0.699	1.063
RuO_x-Pt₃Zn	0.431	‒0.504	0.686

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RuO_x-PtZn催化剂加速水活化过程实现高效的直接甲醇燃料电池

RuO_x-PtZn catalyst boosting methanol electro-oxidation by synergic water-activation for high-performance direct methanol fuel cell

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RuOx-PtZn催化剂加速水活化过程实现高效的直接甲醇燃料电池

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RuO_x-PtZn催化剂加速水活化过程实现高效的直接甲醇燃料电池

RuO_x-PtZn catalyst boosting methanol electro-oxidation by synergic water-activation for high-performance direct methanol fuel cell