快速配体转换制备高密度Ir单原子用于高效催化酸性水氧化

doi:10.1016/S1872-2067(24)60128-2

催化学报 ›› 2024, Vol. 66: 223-232.DOI: 10.1016/S1872-2067(24)60128-2

快速配体转换制备高密度Ir单原子用于高效催化酸性水氧化

施兆平^a^,^b, 王子昂^a^,^b, 吴鸿翔^a^,^b, 肖梅玲^a^,^b^,^*(), 刘长鹏^a^,^b^,^*(), 邢巍^a^,^b^,^*()

^a中国科学院长春应用化学研究所, 电分析化学国家重点实验室, 吉林省低碳化学电源实验室, 吉林长春 130022
^b中国科学技术大学应用化学与工程学院, 安徽合肥 230026

收稿日期:2024-07-16 接受日期:2024-08-29 出版日期:2024-11-18 发布日期:2024-11-10
通讯作者: *电子信箱: mlxiao@ciac.ac.cn (肖梅玲);liuchp@ciac.ac.cn (刘长鹏);xingwei@ciac.ac.cn (邢巍).
基金资助:
国家重点研发项目(2022YFB4002000);国家自然科学基金(22232004);中国科学院战略性先导科技专项(XDA0400301);吉林省科技发展项目(20210301008GX);吉林省科技发展项目(20210502002ZP);吉林省科技发展项目(20240101019JC);吉林省发展改革委员会项目(2023C032-6)

High-density Ir single sites from rapid ligand transformation for efficient water electrolysis

Zhaoping Shi^a^,^b, Ziang Wang^a^,^b, Hongxiang Wu^a^,^b, Meiling Xiao^a^,^b^,^*(), Changpeng Liu^a^,^b^,^*(), Wei Xing^a^,^b^,^*()

^aState Key Laboratory of Electroanalytic Chemistry, Jilin Province Key Laboratory of Low Carbon Chemistry Power, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, Jilin, China
^bSchool of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026, Anhui, China

Received:2024-07-16 Accepted:2024-08-29 Online:2024-11-18 Published:2024-11-10
Contact: *E-mail: mlxiao@ciac.ac.cn (M. Xiao),liuchp@ciac.ac.cn (C. Liu),xingwei@ciac.ac.cn (W. Xing).
Supported by:
National Key R&D Program of China(2022YFB4002000);National Natural Science Foundation of China(22232004);Strategic Priority Research Program of the Chinese Academy of Sciences(XDA0400301);Jilin Province Science and Technology Development Program(20210301008GX);Jilin Province Science and Technology Development Program(20210502002ZP);Jilin Province Science and Technology Development Program(20240101019JC);Jilin Province Development and Reform Commission Program(2023C032-6)

摘要/Abstract

摘要：

与可再生能源耦合的质子交换膜电解水制氢(PEMWE)是实现零碳排放绿氢制备的关键技术, 具有电解效率高、产氢纯度高等诸多优势. 阳极侧氧析出反应(OER)动力学缓慢、反应过电势高, 需要使用的大量贵金属铱(Ir), 这严重阻碍了PEMWE技术的规模化应用. 为了降低贵金属Ir用量, 减少对稀缺Ir资源的依赖, 开发具有高催化活性位点利用率的低Ir含量催化剂具有重要意义. 为了实现该目标, 研究人员设计了氧化物负载的Ir基催化剂、Ir基合金/氧化物催化剂以及Ir单原子催化剂, 其中Ir单原子催化剂可以大幅降低贵金属用量, 因而受到广泛关注. 然而, 单原子催化剂存在活性位点密度低的短板, 在实际PEMWE电解槽中的性能表达欠佳. 因此, 发展具有高活性位点密度的Ir单原子催化剂势在必行.

本文发展了一种具有高活性位点密度的Ir单原子催化剂, 解决了Ir单原子催化剂性能无法在PEMWE电解槽中高效表达的问题. 通过NaNO₃辅助直接热解法在MnO₂基底上制备得到了Ir原子密度为4.22 atom nm^-2的高密度Ir单原子催化剂(记作NaNO₃-H-Ir-MnO₂). X射线衍射、高角环形暗场扫描透射电镜、X射线光电子能谱及X射线吸收谱结果表明, 高密度的Ir单原子均匀分布在MnO₂基底上, 形成了Mn-O-Ir-O-Mn的局域配位结构. 与无NaNO₃添加制备的低密度Ir单原子催化剂(记作L-Ir-MnO₂, 0.84 atom nm^-2)相比, NaNO₃-H-Ir-MnO₂样品中的Ir单原子密度增加5倍以上. 热分解过程进行原位拉曼光谱测试, 结合热重分析实验结果表明, NaNO₃促进了前驱体中Ir-Cl配位结构向Ir-O配位结构的快速转变, 使其与MnO₂晶相结构的形成同时发生, 保证了高密度Ir位点在MnO₂基底中的均匀分散. 拉曼光谱结果表明, 在热分解反应进行30 s后, 随着前驱体中NaNO₃添加量的增大, Ir-Cl配位对应的拉曼散射峰(160-190 cm^-1)强度逐渐下降, 最终完全消失. 热重分析结果表明, 前驱体中添加NaNO₃一方面抑制了Mn(NO₃)₂热解形成MnO₂的过程, 热分解温度由226 ºC升至236 ºC; 另一方面, 将前驱体中Ir-Cl配位向Ir-O配位结构转变温度由~430 ºC降至~210 ºC. 这种热分解温度的变化直接导致了前驱体中Ir-O与Mn-O配位结构同步形成, 进而保证了样品中Ir原子的均匀分散, 最终得到高密度Ir单原子催化剂. 三电极体系中的电化学测试结果表明, 尽管NaNO₃-H-Ir-MnO₂与L-Ir-MnO₂样品的OER催化本征活性相同, 但由于活性位点密度提升, NaNO₃-H-Ir-MnO₂表观催化性能显著改善, 电流密度达到10 mA cm^-2时过电位仅为214 mV, 较L-Ir-MnO₂降低了25 mV. 以所制备的Ir单原子催化剂为阳极组装PEMWE电解槽, 性能测试结果表明, NaNO₃-H-Ir-MnO₂与L-Ir-MnO₂样品在低电流密度(< 0.1 A cm^-2)区的性能接近, 但随着电流密度提升性能差异显著. 在1.9 V电解电压下, 以NaNO₃-H-Ir-MnO₂为阳极的电解槽电流密度达到3.5 A cm^-2, 是L-Ir-MnO₂以及商业Umicore催化剂的3.07倍和1.57倍, 超过了美国DOE2025目标(3 A cm^-2@1.9 V). 该结果证明了提升Ir单原子催化剂活性位点密度可以优化其在PEMWE电解槽中高氧化电位大电流密度下的性能.

综上, 本工作通过NaNO₃辅助法调制热分解过程中的配体转化步骤, 制备了一种高活性位点密度的Ir单原子催化剂, 在PEMWE电解槽大电流密度下实现了高效性能表达, 为设计可用于实际电解器件的低Ir用量高效催化剂提供了新的思路.

关键词: 酸性析氧反应, 高密度Ir单原子位点, 原位拉曼光谱, PEM电解槽, 配体转换

Abstract:

The development of high-performance oxygen evolution reaction catalysts with low iridium content is the key to the scale-up of proton exchange membrane water electrolyzer (PEMWE) for green hydrogen production. Single-site electrocatalysts with maximized atomic efficiency are held as promising candidates but still suffer from inadequate activity and stability in practical electrolyzer due to the low site density. Here, we proposed a NaNO₃-assistant thermal decomposition strategy for the preparation of high-density Ir single sites on MnO₂ substrate (NaNO₃-H-Ir-MnO₂). Direct spectroscopic evidence suggests the inclusion of NaNO₃ accelerates the transformation of Ir-Cl to Ir-O coordination, thus generating uniform dispersed high-density Ir single sites in the products. The optimized H-Ir-MnO₂ demonstrates not only high intrinsic activity in a three-electrode set-up but also boosted performance in scalable PEMWE, requiring a cell voltage of only 1.74 V to attain a high current density of 2 A cm^-2 at a low Ir loading of 0.18 mg_Ir cm^-2. This work offers a new insight for enhancing the industrial practicality of Ir-based single site catalysts.

Key words: Acidic oxygen evolution reaction, High-density Ir single sites, In situ Raman spectroscopy, Proton exchange membrane electrolyzer, Ligand transformation

施兆平, 王子昂, 吴鸿翔, 肖梅玲, 刘长鹏, 邢巍. 快速配体转换制备高密度Ir单原子用于高效催化酸性水氧化[J]. 催化学报, 2024, 66: 223-232.

Zhaoping Shi, Ziang Wang, Hongxiang Wu, Meiling Xiao, Changpeng Liu, Wei Xing. High-density Ir single sites from rapid ligand transformation for efficient water electrolysis[J]. Chinese Journal of Catalysis, 2024, 66: 223-232.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60128-2

https://www.cjcatal.com/CN/Y2024/V66/I11/223

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Fig. 1. Preparation scheme and the structure of Ir doped MnO2. (a) Schematic illustration of catalyst fabrication method; (b) XRD patterns of γ-MnO2, L-Ir-MnO2, H-Ir-MnO2 and NaNO3-H-Ir-MnO2; (c) TEM and (d) HRTEM image of NaNO3-H-Ir-MnO2; (e,f) HAADF-STEM images of NaNO3-H-Ir-MnO2, the orange box in (f) indicates a randomly selected square with an area of 7 nm × 7 nm and the red circle indicates the Ir sites within that area; (g) the FT-EXAFS and the corresponding fitting results for NaNO3-H-Ir-MnO2 and IrO2.

Fig. 2. In situ Raman analyze. The in situ Raman spectrum of the precursor aqueous containing 100%Mn(NO3)2 (a), 3%H2IrCl6 + 97%Mn(NO3)2 (b), 7%H2IrCl6 + 93%Mn(NO3)2 (c), 7%H2IrCl6 + 93%Mn(NO3)2 + 20%NaNO3 (d). The spectrum obtained after 150 s (e) and 30 s (f) reaction at 220 °C. (g) The evolution of the Raman intensity of Ir-Cl scattering with varied H2IrCl6 and NaNO3 content.

Fig. 3. Schematic diagram of the structure formation process of Ir doped MnO2. Formation process of L-Ir-MnO2 (a), H-Ir-MnO2 (b), and NaNO3-H-Ir-MnO2 (c).

Fig. 4. OER catalytic performance in three-electrode set-up. (a) LSV curves of NaNO3-H-Ir-MnO2 and the controls normalized by the geometric area of electrode; (b) comparison on the mass activity of NaNO3-H-Ir-MnO2 and the recent reported Ir-based catalysts; (c) comparison on the TOF of NaNO3-H-Ir-MnO2 and the recent reported Ir-based catalysts; (d) the Tafel plots and (e) EIS spectrum (@1.445 V vs. RHE) of NaNO3-H-Ir-MnO2 and the controls; (f) Arrhenius plots of NaNO3-H-Ir-MnO2 and the controls; (g) chronopotentiometric responds of NaNO3-H-Ir-MnO2 and Ir-MnO2 at 100 mA cm-2; (h) chronoamperometric responds of NaNO3-H-Ir-MnO2 at 1.5 V and 1.6 V vs. RHE.

Fig. 5. Performance of NaNO3-H-Ir-MnO2 in PEMWE electrolyer. (a) Steady-state polarization curves of electrolyzer constructed with NaNO3-H-Ir-MnO2 at different Ir loading; (b) comparison on the Ir mass activity of the electrolyzer constructed with NaNO3-H-Ir-MnO2 and the recently reported Ir-based catalysts; (c) chronopotentiometry curve of the PEM electrolyzer using NaNO3-H-Ir-MnO2 operated at 0.5 A cm-2 at 60 °C.

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快速配体转换制备高密度Ir单原子用于高效催化酸性水氧化

High-density Ir single sites from rapid ligand transformation for efficient water electrolysis

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