安培级电流密度下淬火优化CoPS纳米棒的晶型/非晶型比例以促进肼辅助的全水分解

doi:10.1016/S1872-2067(24)60044-6

催化学报 ›› 2024, Vol. 62: 265-276.DOI: 10.1016/S1872-2067(24)60044-6

安培级电流密度下淬火优化CoPS纳米棒的晶型/非晶型比例以促进肼辅助的全水分解

陈晓^a^,^b, 杜云梅^a^,^c^,^*(), 杨宇^a^,^b, 刘康^a^,^b, 赵晋灵^d, 夏晓丹^d, 王磊^a^,^c^,^*()

^a青岛科技大学生态化学工程教育部重点实验室, 生态化学工程与绿色制造国际科技合作基地, 山东青岛 266042
^b青岛科技大学化学与分子工程学院, 山东青岛 266042
^c青岛科技大学环境与安全工程学院, 山东青岛 266042
^d青岛海发环保产业控股有限公司, 山东青岛 266000

收稿日期:2024-04-11 接受日期:2024-04-16 出版日期:2024-07-18 发布日期:2024-07-10
通讯作者: *电子信箱: duyunmeiqust@163.com (杜云梅), inorchemwl@126.com (王磊).
基金资助:
国家自然科学基金(52072197);国家自然科学基金(52302274);111工程(D20017);山东省优秀青年基金(ZR2019JQ14);山东省自然科学基金(ZR2022QE098);科技创新重大专项(2019JZZY020405);山东省自然科学基金重大基础研究项目(ZR2020ZD09);山东博士后创新项目(SDCX-ZG-20220307);青岛市博士后应用研究项目(04030431060100);山东省双百人才计划(WST2020003)

Quenching to optimize the crystalline/amorphous ratio of CoPS nanorods for hydrazine-assisted total water decomposition at ampere-level current density

Xiao Chen^a^,^b, Yunmei Du^a^,^c^,^*(), Yu Yang^a^,^b, Kang Liu^a^,^b, Jinling Zhao^d, Xiaodan Xia^d, Lei Wang^a^,^c^,^*()

^aKey Laboratory of Eco-chemical Engineering, Ministry of Education, International Science and Technology Cooperation Base of Eco-chemical Engineering and Green Manufacturing, Qingdao University of Science and Technology, Qingdao 266042, Shandong, China
^bCollege of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, Shandong, China
^cCollege of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao 266042, Shandong, China
^dQingdao Haifa Environmental Protection Industry Holdings Co., Ltd. Qingdao 266000, Shandong, China

Received:2024-04-11 Accepted:2024-04-16 Online:2024-07-18 Published:2024-07-10
Contact: *E-mail: duyunmeiqust@163.com (Y. Du), inorchemwl@126.com (L. Wang).
Supported by:
National Natural Science Foundation of China(52072197);National Natural Science Foundation of China(52302274);111 Project of China(D20017);Outstanding Youth Foundation of Shandong Province, China(ZR2019JQ14);Natural Science Foundation of Shandong Province, China(ZR2022QE098);Major Scientific and Technological Innovation Project(2019JZZY020405);Major Basic Research Program of Natural Science Foundation of Shandong Province under Grant(ZR2020ZD09);Postdoctoral Innovation Project of Shandong Province(SDCX-ZG-20220307);Qingdao Postdoctoral Researcher Applied Research Project(04030431060100);Double-Hundred Talent Plan of Shandong Province(WST2020003)

摘要/Abstract

摘要：

近年来, 具有独特电子效应和协同效应的异质界面工程策略在扩展催化功能和提高本征活性方面显示出较大的应用潜力. 其中, 具有晶型/无定形(c/a)异质结构的电催化剂, 由于结构上的巨大差异, 展现出显著的催化活性. 然而, c/a-异质界面的可控调控及其与电催化性能的内在联系仍缺乏系统研究. 因此, 本文采用“酸刻蚀-气相磷硫化-淬火”方法, 合成了具有可调控c/a异质界面的q-CoPS材料, 并将其应用于碱性整体水分解. 同时, 通过控制淬火的初始温度, 实现了对CoPS纳米棒中c/a比例的有效调控.

一般来说, 在晶型材料中, 表面催化往往发生在固定的晶面上. 而无定形材料可以同时满足体积和表面的催化. 同时, 无定形材料具有柔韧性, 在催化反应过程中可以转化为任何需要的其他形式, 因此在耐腐蚀方面也具有较好的自愈性能. 此外, 无定形材料还具有丰富的缺陷, 运用缺陷工程可以带来一定的性能提升. 因此, 二者的协同作用可以提升催化剂的催化性能. 本文创新性地提出了通过改变淬火初始温度对CoPS纳米棒中c/a比进行调控. 采用“酸刻蚀-气相磷硫化-淬火”方法, 成功制备了具有独特c/a-CoPS核壳异质结构的q-CoPS纳米棒. 随着淬火初始温度的升高, 无定形CoPS壳的面积也在逐渐增大. 这可能是由于处于非平衡状态的磷硫化物在超低温液氮中突然淬火, 处于热运动的Co, P和S原子会迅速冷却, 趋向于形成无序的CoPS无定形材料. 值得注意的是, 制备得到的q-CoPS纳米棒具有合适的c/a含量比, 提供了丰富的c/a界面活性位点, 并优化了Co位点的电子构型. 在析氢反应(HER)中, q-CoPS/CF仅需90 mV的过电位即可以达到1000 mA cm^‒2的工业级电流密度, 结果优于先进的Pt/C. 同时, q-CoPS/CF在肼氧化反应(HzOR)中, 仅0.06 V时即可实现1000 mA cm^‒2的电流密度. 密度泛函理论计算表明, 在HER和HzOR中, 界面处的Co原子的内在活性远高于P原子和S原子, c/a-异质界面处活性位点的能垒远低于晶型CoPS和无定形CoPS. 此外, Co位点作为c/a界面的双功能活性位点, 有效地优化了HER和HzOR的反应动力学.

综上所述, q-CoPS/CF催化剂电催化性能的提升主要是由于其具备高活性的CoPS、合适的晶型/无定形(c/a)比例和较大的比表面积. 本文为设计具有c/a异质结构的高活性电极提供参考, 为进一步探索c/a异质结构的演化和确定c/a界面的活性位点提供借鉴.

关键词: q-CoPS, c/a-异质结构, 淬火, 析氢反应, 肼氧化反应

Abstract:

Directional construction of crystalline/amorphous (c/a)-phosphosulfide heterostructures with exceptional intrinsic activity through a facile strategy is challenging. In this study, we synthesized q-CoPS nanorods with a unique c/a-CoPS core-shell heterostructure through the ‘gas-phase phosphorus vulcanization-quenching’ treatment. This work also innovatively masters the regulation of the initial quenching temperature to alter the c/a ratio of the CoPS nanorods. Surprisingly, with increasing initial quenching temperature, the area of the amorphous CoPS shell gradually increases. Density functional theory calculations reveal that the Co sites at the c/a-heterointerface, as the difunctional c/a-interface active site, effectively optimize the kinetics of the hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HzOR). As anticipated, q-CoPS/CF requires an overpotential of only 90 mV at a current density of 1000 mA cm^-2 for the alkaline HER, which is much lower than that required using the state-of-the-art Pt/C catalyst. Additionally, q-CoPS/CF achieves a current density of 1000 mA cm^-2 at only 0.06 V in the HzOR. Overall, this work proposes an efficient strategy for developing a bifunctional electrocatalyst with a unique c/a-heterostructure to address future energy needs.

Key words: q-CoPS, c/a-heterostructures, Quenching, Hydrogen evolution reaction, Hydrazine oxidation reaction

陈晓, 杜云梅, 杨宇, 刘康, 赵晋灵, 夏晓丹, 王磊. 安培级电流密度下淬火优化CoPS纳米棒的晶型/非晶型比例以促进肼辅助的全水分解[J]. 催化学报, 2024, 62: 265-276.

Xiao Chen, Yunmei Du, Yu Yang, Kang Liu, Jinling Zhao, Xiaodan Xia, Lei Wang. Quenching to optimize the crystalline/amorphous ratio of CoPS nanorods for hydrazine-assisted total water decomposition at ampere-level current density[J]. Chinese Journal of Catalysis, 2024, 62: 265-276.

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图/表 6

Fig. 1. Morphology and structural characterization of CoPS/CF and q-CoPS/CF. (a) Schematic illustration of the synthesis process; (b,c) SEM images; (d,e) TEM images; (f,g) HRTEM images; (h) HAADF-STEM and the corresponding EDX mapping images.

Fig. 2. Structure characterization. Total XPS spectra (a) and S 2p (b), Co 2p (c), and P 2p (d) XPS spectra.

Fig. 3. HER performance in 1.0 mol L-1 KOH. (a) Polarization curves. (b) Overpotentials at a current density of 10, 100, and 500 mA cm-2. (c) Tafel slopes of different catalysts obtained from the polarization curves in (a). (d) Nyquist plots. (e) Dependence of the average capacitive currents on scan rate. (f) Comparison of η10 of recently reported noble metal-based electrocatalysts for the HER.

Fig. 4. HzOR performance of q-CoPS/CF and its counterparts in alkaline solution. (a) LSV curves of the HzOR and OER. (b) HzOR and OER overpotential at 10-500 mA cm?2. (c) LSV curves. (d) Overpotential at 10, 100, 1000, and 2000 mA cm?2. (e) Tafel slopes. (f) Nyquist plots. (g) Comparison of overpotentials at 10 mA cm?2 of the recently reported catalysts. (h) Multi-steps chronopotentiometry curves for q-CoPS/CF tested at different current densities.

Fig. 5. (a) Model diagram of a-CoPS and c-CoPS structures of the q-CoPS catalyst. (b) ΔGH* of Co at the a-CoPS site, c-CoPS site, and c/a-interface. (c) ΔG of Co at the a-CoPS site, c-CoPS site, and c/a-interface. (d) ΔGH* and (e) ΔG on the Co, P, and S sites.

Fig. 6. OHzS performance of q-CoPS/CF ‖ q-CoPS/CF and the counterparts in alkaline solution. (a) LSV curves of q-CoPS for OHzS and OWS. (b) Overpotential of q-CoPS for OHzS and OWS at 10-500 mA cm?2. (c) LSV curves. (d) Multi-step chronopotentiometry curves for q-CoPS/CF ‖ q-CoPS/CF tested at different current densities. (e) Solar energy-driven OHzS and OWS in q-CoPS/CF ‖ q-CoPS/CF. (f) Comparison of the overpotentials at 10 mA cm?2 of the recently reported catalysts.

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安培级电流密度下淬火优化CoPS纳米棒的晶型/非晶型比例以促进肼辅助的全水分解

Quenching to optimize the crystalline/amorphous ratio of CoPS nanorods for hydrazine-assisted total water decomposition at ampere-level current density

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