原子轨道调节的MOF衍生结构的双功能双金属磷化物用于促进高效的整体水分解

doi:10.1016/S1872-2067(24)60124-5

催化学报 ›› 2024, Vol. 65: 113-125.DOI: 10.1016/S1872-2067(24)60124-5

原子轨道调节的MOF衍生结构的双功能双金属磷化物用于促进高效的整体水分解

安博涵^a^,^b, 刘威龙^a^,^b, 董继鹏^a^,^b, 李宁^a^,^b, 高旸钦^a^,^b, 戈磊^a^,^b^,^*()

^a中国石油大学新能源与材料学院, 重油加工国家重点实验室, 北京102249
^b中国石油大学新能源与材料学院, 材料科学与工程系, 北京102249

收稿日期:2024-06-10 接受日期:2024-07-22 出版日期:2024-10-18 发布日期:2024-10-15
通讯作者: *电子信箱: gelei@cup.edu.cn (戈磊).
基金资助:
国家自然科学基金(52473327);国家自然科学基金(51572295);国家自然科学基金(21273285);国家自然科学基金(21003157);国家重点研发计划(2021YFA1501300);国家重点研发计划(2019YFC1907602)

Atomic orbitals modulated dual functional bimetallic phosphides derived from MOF on MOF structure for boosting high efficient overall water splitting

Bohan An^a^,^b, Weilong Liu^a^,^b, Jipeng Dong^a^,^b, Ning Li^a^,^b, Yangqin Gao^a^,^b, Lei Ge^a^,^b^,^*()

^aState Key Laboratory of Heavy Oil Processing, College of New Energy and Materials, China University of Petroleum Beijing, Beijing 102249, China
^bDepartment of Materials Science and Engineering, College of New Energy and Materials, China University of Petroleum Beijing, Beijing 102249, China

Received:2024-06-10 Accepted:2024-07-22 Online:2024-10-18 Published:2024-10-15
Contact: *E-mail: gelei@cup.edu.cn (L. Ge).
Supported by:
National Natural Science Foundation of China(52473327);National Natural Science Foundation of China(51572295);National Natural Science Foundation of China(21273285);National Natural Science Foundation of China(21003157);National Key R&D Program of China(2021YFA1501300);National Key R&D Program of China(2019YFC1907602)

摘要/Abstract

摘要：

近年来, 面对当前的全球能源和碳排放问题, 氢燃料因其高能量密度(140 MJ kg^-1)和零碳排放而被认为是取代化石燃料的最有前景的能源之一. 其中, 利用电化学水分解产生的绿氢是最环保、最友好的方法. 然而, 电化学析氢需要同时发生两个半反应(析氢反应(HER)和析氧反应(OER)), 由于OER反应是四步质子耦合电子转移过程, 其缓慢的动力学显著阻碍了其能量转换效率. 为了解决上述问题, 需要设计合成双功能催化剂, 以实现精确的电荷调制和电子再分配的协同效应.

本文从金属有机框架(MOF)材料结构上合理设计和合成了双金属磷化物, 以实现精确的电荷调制和电子再分配的协同效应, 从而显著提升催化性能. 具体而言, 通过两步溶剂热外延生长工艺, 获得了具有金属有机框架在另一金属有机框架结构的MIL-88(Fe)@ZIF-67前体. 再通过原位磷化工艺制备了双金属磷化物. 两种MOFs的相位共轭和金属中心的协同效应对电子分布有调节作用, 其更大的比表面积暴露出更多的活性位点. 值得注意的是, FeP和CoP₃之间产生的异质结界面促进了电子转移, 丰富了活性位点并调节了电子结构, 从而实现了较好的电催化性能, 远优于单一MOF前体合成的磷化物. 实验和理论计算结果表明, Fe和Co离子之间的协同作用可以有效地降低速率测定步骤(RDS)的能垒, 从而提高催化活性, 降低OER活化能(E_a). 高效金属磷化物电催化剂的电子调制特性可用于调节OER的性能. 电化学测试结果表明, 具有金属有机框架在另一金属有机框架结构的催化剂也可以提高整体水分解性能. 原子轨道理论和密度泛函理论计算结果表明, 在MOF结构上使用MOF合成工艺的FeP-CoP₃双金属磷化物成功调制了电子轨道分布. 该调节现象是由于两种类型的MOFs的相位共轭和金属中心Co物种的协同作用, 从而导致材料基质中形成配位不饱和Co和Fe原子, 这些原子反而成为氧分子捕获的关键位点, 促进了O-O键的合成, 降低了OER的反应能垒. 因此, 该催化剂表现出较好的电催化活性, 在析氢反应测试时, 在电流密度为10 mA cm^‒2条件下, 表现为81 mV低过电位; 而在析氧反应测试时, 在电流密度为50 mA cm^‒2条件下, 表现为239 mV低过电位. 对于水的整体分解, 双功能电催化剂FeP-CoP₃偶联的双电极碱性电解池只需要1.49 V (η50), 并且可以在50 h内保持较好的电催化能力.

综上, 利用两步溶剂热外延生长工艺合成了具有金属有机框架在另一金属有机框架结构的双金属磷化物催化剂, 有效克服了电化学过程中OER反应的动力缓慢所造成的催化效率较低等问题, 并有效地提升了催化剂的全解水性能, 为设计高性能的电催化产氢材料提供了一定参考.

关键词: 金属磷化物, MoF on MoF结构, 原子轨道理论, 密度泛函理论计算

Abstract:

The electronic modulation characteristics of efficient metal phosphide electrocatalysts can be utilized to tune the performance of oxygen evolution reaction (OER). However, improving the overall water splitting performance remains a challenging task. By building metal organic framework (MOF) on MOF heterostructures, an efficient strategy for controlling the electrical structure of MOFs was presented in this study. ZIF-67 was in-situ synthesized on MIL-88 (Fe) using a two-step self-assembly method, followed by low-temperature phosphorization to ultimately synthesize FeP-CoP₃ bimetallic phosphides. By combining atomic orbital theory and theoretical calculations (density functional theory), the results reveal the successful modulation of electronic orbitals in FeP-CoP₃ bimetallic phosphides, which are synthesized from MOF on MOF structure. The synergistic impact of the metal center Co species and the phase conjugation of both kinds of MOFs are responsible for this regulatory phenomenon. Therefore, the catalyst demonstrates excellent properties, demonstrating HER 81 mV (η10) in a 1.0 mol L^-1 KOH solution and OER 239 mV (η50) low overpotentials. The FeP-CoP₃ linked dual electrode alkaline batteries, which are bifunctional electrocatalysts, have a good electrocatalytic ability and may last for 50 h. They require just 1.49 V (η50) for total water breakdown. Through this technique, the electrical structure of electrocatalysts may be altered to increase catalytic activity.

Key words: Transition metal phosphides, MOF on MOF, Atomic orbital theory, Density functional theory calculation

安博涵, 刘威龙, 董继鹏, 李宁, 高旸钦, 戈磊. 原子轨道调节的MOF衍生结构的双功能双金属磷化物用于促进高效的整体水分解[J]. 催化学报, 2024, 65: 113-125.

Bohan An, Weilong Liu, Jipeng Dong, Ning Li, Yangqin Gao, Lei Ge. Atomic orbitals modulated dual functional bimetallic phosphides derived from MOF on MOF structure for boosting high efficient overall water splitting[J]. Chinese Journal of Catalysis, 2024, 65: 113-125.

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图/表 8

Fig. 1. (a) SEM image of FeP-CoP3. (b) TEM images of FeP-CoP3. (c-e) HRTEM images of FeP-CoP3. (f) SAED image of FeP-CoP3. (g-m) EDS elemental mapping images for Co, Fe, P, O, N, C separately.

Fig. 2. (a) Process flowchart for preparing MOF on MOF structure. XRD images of FeP-CoP3 (b), FeP and CoP3 (c), Co3O4 and Fe2O3 (d). (e) Partial enlarged XRD images of FeP-CoP3. (f) SBET image of FeP-CoP3, FeP and CoP3. (g) Raman images of FeP-CoP3, FeP and CoP3. (h) Comparison graph of Fe XPS peaks. (i) Comparison graph of Co XPS peaks. (j) Comparison graph of P XPS peaks.

Fig. 3. (a) The LSV curves of FeP-CoP3, FeP, Fe2O3, CoP3, Co3O4 and CG. (b) Tafel slops of FeP-CoP3, FeP, Fe2O3, CoP3, Co3O4 and CG. (c) Relevant overpotentials at η10, η50 and η100 of the samples. (d,e) Impedance of the prepared catalyst. (f) HER stability test of FeP-CoP3. (g) Comparison of HER performance with other catalysts. (h) Comparison of HER LSV before and after stability testing.

Fig. 4. (a) LSV curves of FeP-CoP3, FeP, Fe2O3, CoP3, Co3O4 and CG. (b) Tafel slops of FeP-CoP3, FeP, Fe2O3, CoP3, Co3O4 and CG. (c) Relevant overpotentials at η50, η100 and η150 of the samples; (d,e) Impedance of the prepared catalyst. (f) OER stability test of FeP-CoP3. (g) Comparison of OER performance with other catalysts. (h) Comparison of OER LSV before and after stability testing.

Fig. 5. (a) Overall water splitting LSV curves of as-prepared catalysts at 1 M KOH. (b) FeP-CoP3 catalytic stability. (c) XRD pattern of FeP-CoP3 recovered for OER reaction. (d) Activity comparison with other electrocatalysts.

Fig. 6. (a) Free energy diagram of HER intermediates at different U values, and bottom image is most likely OER mechanism, Gibbs free energy profiles along the reaction pathway of CoP3 (b), FeP (c), and FeP-CoP3 (d).

Fig. 7. Density of states projected on the d-states of Fe in Fe-CoP3 (a), Co in FeP-CoP3 (b), Fe in FeP (c), and Co in CoP3 (d). Dashed-dotted lines and the numbers show the position of d-band center. Eg density of states projected on the d-states of Fe in Fe-CoP3 (e), Co in FeP-CoP3 (f), Fe in FeP (g), Co in CoP3 (h). (i) The charge density difference between FeP-CoP3. Charge buildup and depletion are represented by the colors blue and yellow, respectively. (j) Schematic diagram of OER process.

Fig. 8. Schematics of d-orbital electronic configurations of central metals in single atom Fe (a), single atom Co (b), and FeP-CoP3 (c) [43].

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原子轨道调节的MOF衍生结构的双功能双金属磷化物用于促进高效的整体水分解

Atomic orbitals modulated dual functional bimetallic phosphides derived from MOF on MOF structure for boosting high efficient overall water splitting

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