磷掺杂碳负载ZnxPyOz常温常压下高效电催化合成氨

引用本文: 王佳, 秦清, 王哲, 赵旭浩, 陈云菲, 候利强, 刘尚果, 刘希恩. 磷掺杂碳负载Zn_xP_yO_z常温常压下高效电催化合成氨[J]. 物理化学学报, 2024, 40(3): 230404. doi: 10.3866/PKU.WHXB202304044 shu

Citation: Jia Wang, Qing Qin, Zhe Wang, Xuhao Zhao, Yunfei Chen, Liqiang Hou, Shangguo Liu, Xien Liu. P-Doped Carbon-Supported Zn_xP_yO_z for Efficient Ammonia Electrosynthesis under Ambient Conditions[J]. Acta Physico-Chimica Sinica, 2024, 40(3): 230404. doi: 10.3866/PKU.WHXB202304044 shu

磷掺杂碳负载Zn_xP_yO_z常温常压下高效电催化合成氨

青岛科技大学化工学院, 山东青岛 266042

通讯作者: 秦清, qinqing@qust.edu.cn; 刘希恩, liuxien@qust.edu.cn

基金项目:
山东省泰山学者人才工程 ts201712045

山东省泰山学者人才工程 tsqn202211162

国家自然科学基金 22102079

山东省自然科学基金 ZR2021YQ10

摘要: 合成氨(NH₃)的发展是现代工业进程和人类生存的基石。受氮气(N₂)化学惰性的限制，当前的合成氨工业能源消耗高并且排放大量的二氧化碳。电化学氮气还原反应(NRR)，是有望取代高能耗的Haber-Bosch (HB)合成法的一种绿色可持续的合成氨工艺。然而，因氮气以及析氢竞争副反应(HER)导致电催化氮气还原极低的NH₃产率和能量转换效率一直是目前人工固氮领域面临的挑战。在本文中，我们报道了一种具有丰富孔结构的磷掺杂碳(PC)负载Zn₃(PO₄)₂/Zn₂P₂O₇纳米复合材料(h-PC/Zn₃(PO₄)₂/Zn₂P₂O₇)，在酸性和中性介质中将N₂高效催化转化为NH₃。其独特的分级多孔结构提高了表面粗糙度并加快了氮气在催化剂体相中的扩散，这有利于延长氮气在催化剂表面的停留时间以及提高活性位点的利用效率；而多组分的均匀分布可以调节电子结构并优化反应中间体的吸附行为，进而提高活性位点的本征活性。在0.1 mol∙L⁻¹ HCl电解液中，h-PC/Zn₃(PO₄)₂/Zn₂P₂O₇在−0.2 V vs.可逆氢电极(RHE)电位下NH₃的产率可以达到38.7 ± 1.2 μg∙h⁻¹∙mg_cat⁻¹，法拉第效率为19.8% ± 0.9%。此外，h-PC/Zn₃(PO₄)₂/Zn₂P₂O₇在0.1 mol∙L⁻¹ Na₂SO₄溶液中同样展现出优异的电催化氮气还原合成氨性能，NH₃产率及法拉第效率分别为17.1 ± 0.8 μg∙h⁻¹∙mg_cat⁻¹和15.9% ± 0.6%，明显优于PC/Zn₃P₂、C/ZnO和大多数报道的非贵金属电催化剂。这种优异的性能主要归因于多孔结构有利于传质及多组分活性位点协同效应。此外，我们采用非原位X射线光电子能谱(XPS)、透射电子显微镜(TEM)和X射线衍射(XRD)等表征手段对NRR测试前后h-PC/Zn₃(PO₄)₂/Zn₂P₂O₇的组成和结构变化进行了剖析。在反应后检测到了新增的N物种信号，证明催化剂表面确实发生了氮气还原反应。本研究提供了一种通过同步构建传质通道并耦合不同的活性位点以协同增强NRR活性和选择性的新思路，这对加快绿色制氨工业化具有重大意义。

关键词:

English

P-Doped Carbon-Supported Zn_xP_yO_z for Efficient Ammonia Electrosynthesis under Ambient Conditions

College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, Shandong Province, China

Corresponding author: Email: qinqing@qust.edu.cn (Q.Q.); Email: liuxien@qust.edu.cn (X.L.)

Received Date: 24 April 2023
Accepted Date: 14 June 2023
Revised Date: 13 June 2023
Available Online: 15 March 2024
Fund Project:
the Taishan Scholar Program of Shandong Province

the Taishan Scholar Program of Shandong Province

the National Natural Science Foundation of China

the Natural Science Foundation of Shandong Province

Abstract: The development of efficient synthetic routes for ammonia (NH₃) production is the cornerstone of the modern industrial processes and human survival. Owing to the chemical inertness of nitrogen, the current ammonia industry suffers from high energy consumption and high CO₂ emission. Electrochemical nitrogen reduction reaction (NRR) provides a promising alternative to the energy-intensive Haber-Bosch (HB) process, enabling green and sustainable NH₃ production. However, a low NH₃ yield and limited energy conversion efficiency due to the chemical inertness of N₂ and competitive hydrogen evolution reaction (HER) are still critical challenges in artificial nitrogen fixation using the electrochemical NRR. Herein, we report a hole-enriched P-doped carbon (PC)-supported Zn₃(PO₄)₂/Zn₂P₂O₇ nanocomposite (h-PC/Zn₃(PO₄)₂/Zn₂P₂O₇) for efficient electrocatalytic conversion of N₂ to NH₃ in both acidic and neutral media. Remarkably, the unique hierarchical porous structure of the h-PC/Zn₃(PO₄)₂/Zn₂P₂O₇ catalyst improves the surface roughness and facilitates the diffusion of N₂ within the catalyst layer, thereby prolonging the residence time of N₂ and improving the utilization of active sites. The uniform distribution of multiple components modulates the electronic structure of the active sites and optimizes the adsorption behavior of various reaction intermediates, enhancing the intrinsic activity of the catalyst. Benefiting from the porous structure and multicomponent active sites, including the Zn species and PC, the h-PC/Zn₃(PO₄)₂/Zn₂P₂O₇ achieves an excellent NRR performance with an NH₃ yield rate of 38.7 ± 1.2 μg∙h⁻¹∙mg_cat⁻¹ and Faradaic efficiency (FE) of 19.8% ± 0.9% at −0.2 V vs. reversible hydrogen electrode (RHE) in 0.1 mol∙L⁻¹ HCl electrolyte. Moreover, it delivers a high NH₃ yield rate of 17.1 ± 0.8 μg∙h⁻¹∙mg_cat⁻¹ with an FE of 15.9% ± 0.6% at −0.2 V vs. RHE in 0.1 mol∙L⁻¹ Na₂SO₄ solution, which is superior to those of PC/Zn₃P₂, C/ZnO, and many other non-noble-metal-based electrocatalysts. Ex situ X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and X-ray diffraction (XRD) studies were conducted to monitor the changes in the composition and structure of h-PC/Zn₃(PO₄)₂/Zn₂P₂O₇ after being used in NRR. In particular, a new signal of N appeared in the XPS profile after NRR, confirming the occurrence of NRR. This work provides a new strategy for synchronously constructing mass transfer channels and coupling different active sites to synergistically enhance the NRR activity and selectivity of a catalyst, which is of great significance in progressing the industrialization of green ammonia production.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

磷掺杂碳负载Zn_xP_yO_z常温常压下高效电催化合成氨

通讯作者: 秦清, qinqing@qust.edu.cn; 刘希恩, liuxien@qust.edu.cn

English

P-Doped Carbon-Supported Zn_xP_yO_z for Efficient Ammonia Electrosynthesis under Ambient Conditions

Corresponding author: Email: qinqing@qust.edu.cn (Q.Q.); Email: liuxien@qust.edu.cn (X.L.)

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

磷掺杂碳负载ZnxPyOz常温常压下高效电催化合成氨

通讯作者: 秦清, qinqing@qust.edu.cn; 刘希恩, liuxien@qust.edu.cn

English

P-Doped Carbon-Supported ZnxPyOz for Efficient Ammonia Electrosynthesis under Ambient Conditions

Corresponding author: Email: qinqing@qust.edu.cn (Q.Q.); Email: liuxien@qust.edu.cn (X.L.)

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

磷掺杂碳负载Zn_xP_yO_z常温常压下高效电催化合成氨

P-Doped Carbon-Supported Zn_xP_yO_z for Efficient Ammonia Electrosynthesis under Ambient Conditions

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