Er掺杂调控CoP活性位点的电子结构促进亚硝酸盐电还原合成氨

doi:10.1016/S1872-2067(24)60224-X

摘要/Abstract

摘要：

氨(NH₃)作为一种重要的无机化工原料, 广泛应用于农业、工业和储能等领域. 目前, 工业上NH₃的生产方法是传统的哈伯-博施工艺.

该工艺反应条件苛刻, 能量耗损高, 并且会同时产生大量的温室气体, 给生态环境带来极大的危害. 电催化亚硝酸盐还原(eNO₂⁻RR)合成NH₃是一种高效、可控且可持续的NH₃合成替代途径, 有望突破传统NH₃合成工艺的限制. 此外, 废水中广泛存在的亚硝酸盐(NO₂⁻)是一种常见的致癌物质, 严重危害环境和人类健康. 然而, 电催化NO₂⁻还原合成NH₃是一个六电子转移过程, 可能产生多种含氮中间产物, 从而影响产物的选择性.

因此, 为了解决能源和环境问题, 合理构建简单、稳定且高效的电催化剂至关重要. 这不仅能实现NH₃的绿色合成, 还能去除废水中有毒的NO₂⁻. 本文开发了一种独特而有效的以稀土金属元素铒(Er)为介导的价电子和表面微环境调控方法. 带有孤对电子的含氮有机配体与带正电荷的Er和金属钴(Co)离子之间的强配位, 确保了通过热解合成的样品中Er和Co位点的强烈耦合. 随后, 通过磷化反应在钛网基底上合成了Er掺杂的磷化钴复合的碳氮纳米片(Er-CoP@NC/TM)催化剂. 值得注意的是, Er的引入调控了Co位点的价电子分布, 使Er-CoP@NC/TM催化剂表现出较好的电催化合成NH₃性能. 在工作电压为−0.8 V vs. RHE时, Er-CoP@NC/TM催化剂获得的最大氨产率达到2087.60 ± 17.10 µmol h^-1 cm^-2; 在工作电压为−0.4 V vs. RHE时, Er-CoP@NC/TM催化剂的最大法拉第效率为97.08 ± 2.22%, 其催化活性远大于原始的磷化钴复合的碳氮纳米片(CoP@NC/TM)催化剂. 此外, Er-CoP@NC/TM催化剂在较宽的NO₂⁻浓度(0.05-0.1 mol L^-1)和pH值(4-13)范围内也表现出卓越的电催化合成NH₃性能. 同时, Er-CoP@NC/TM催化剂在模拟废水环境中表现出较强的抗阴离子干扰能力和较长的循环寿命. 此外, 淬灭实验和电子顺磁共振测试结果表明, 活性氢的直接电催化还原和电子转移对于电催化NO₂⁻合成NH₃至关重要. 实验和理论计算进一步表明, Er的引入调控了Er-CoP@NC/TM催化剂中CoP的电子结构, 从而调节了中间产物的吸附行为以及eNO₂^-RR过程中的决速步骤, 降低了反应能垒, 进一步提高了Er-CoP@NC/TM催化剂合成NH₃的性能.

综上所述, 本研究中通过Er掺杂显著提高了磷化钴复合的碳氮纳米片催化剂的电催化合成NH₃性能, 为修复NO₂⁻废水和回收有价值的NH₃提供了一种新颖实用的解决方案. 同时, 为稀土元素在催化剂的制备和应用方向提供了新思路.

关键词: 电催化, 亚硝酸盐还原, 氨生产, 磷化钴, 铒掺杂

Abstract:

The electrochemical conversion of toxic nitrite (NO₂^-) is a promising approach for the simultaneous removal of nitrogen contaminants and synthesis of ammonia (NH₃). In this study, we present the Er-doping-induced electronic modulation of CoP integrated with nitrogen-doped carbon (CN) nanosheets supported on a titanium mesh (Er-CoP@NC/TM) for the electrocatalytic NO₂^- reduction reaction (eNO₂^-RR) for NH₃ synthesis. The catalyst demonstrates a high Faraday efficiency of 97.08 ± 2.22% and a high yield of 2087.60 ± 17.10 µmol h^-1 cm^-2 for NH₃ production. Characterization and theoretical calculations revealed that Er-doping facilitated the electronic modulation of CoP in Er-CoP@NC/TM, which regulated the adsorption behaviors of intermediates and was the rate-limiting step for the eNO₂^-RR, thereby enhancing the electrocatalytic performance. Quenching experiments and electron paramagnetic resonance tests suggest that both direct electrocatalytic reduction by active hydrogen and electron transfer are critical for the eNO₂^-RR for NH₃ synthesis. Furthermore, Er-CoP@NC/TM exhibited high performance across a wide range of NO₂^- concentrations (0.05-0.1 mol L^-1) and pH values (4-13). In addition, the catalyst demonstrated strong resistance to anions and a long cycle life in simulated wastewater environments. This study offers a powerful approach for the remediation of NO₂^- wastewater and recovery of valuable inorganic compounds.

Key words: Electrocatalysis, Nitrite reduction, Ammonia production, Cobalt phosphide, Er-doping

赵东林, 周科宇, 詹丽, 樊光银, 龙艳, 宋术岩. Er掺杂调控CoP活性位点的电子结构促进亚硝酸盐电还原合成氨[J]. 催化学报, 2025, 70: 299-310.

Donglin Zhao, Keyu Zhou, Li Zhan, Guangyin Fan, Yan Long, Shuyan Song. Modulation of the electronic structure of CoP active sites by Er-doping for nitrite reduction for ammonia electrosynthesis[J]. Chinese Journal of Catalysis, 2025, 70: 299-310.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60224-X

https://www.cjcatal.com/CN/Y2025/V70/I3/299

图/表 8

Fig. 1. (a) Detailed illustration of the fabrication process of Er-CoP@NC/TM. Low (b) and high (c) magnification SEM images, TEM image (insets are particle size distributions) (d), HRTEM image (e), SAED (f), and elemental mappings (g,h) of Er-CoP@NC/TM.

Fig. 2. (a) XRD patterns of CoP@NC/TM and Er-CoP@NC/TM. High resolution XPS spectra of Er 4d (b), Co 2p (c), P 2p (d), C 1s (e), and N 1s (f) for CoP@NC/TM and Er-CoP@NC/TM.

Fig. 3. (a) LSV curves of CoP@NC/TM and Er-CoP@NC/TM in 0.1 mol L-1 KOH with and without 0.1 mol L-1 NO2-. (b) Influences of operating voltages on NH3 yields and FEs in alkaline conditions. (c) NH3 yields and FEs of various electrodes at -0.4 V. (d) NH3 yields and FEs of Er-CoP@NC/TM and previously developed catalysts. (e) FEs of NH3, N2, and H2 of Er-CoP@NC/TM at different electrode potentials. (f) Effects of NO2- concentrations on NH3 yields and FEs with Er-CoP@NC/TM. (g) NH3 yields under various conditions. (h) Electrocatalytic performance of Er-CoP@NC/TM under alternative cycle tests. (i) 1H NMR spectra (600 MHz) of the electrolyte after eNO2-RR at -0.4 V.

Fig. 4. Chronoamperometry curves (a) and cycling performance (b) of Er-CoP@NC/TM for eNO2-RR at -0.4 V. Conversion of NO2- versus electrolysis time (c) and the corresponding FEs and NH3 concentrations (d).

Fig. 5. LSV curves of Er-CoP@NC/TM in 0.1 mol L-1 PBS (a) and in 0.05 mol L-1 H2SO4/0.1 mol L-1 K2SO4 (b) with and without 0.1 mol L-1 NO2-. The NH3 yields and FEs of Er-CoP@NC/TM in neutral (c) and acidic media (d) at different operating voltages.

Fig. 6. (a) NH3 yields and FEs of Er-CoP@NC/TM in NO2- solutions containing different electrolytes. (b) Chronoamperometry curves of Er-CoP@NC/TM during cycling tests at -0.4 V. (c) NH3 yields and FEs of Er-CoP@NC/TM in solutions containing different electrolytes.

Fig. 7. (a) LSV curves with or without tertiary butanol (TBA). (b) EPR spectra of solutions (with or without nitrite) with different c(NO2-) using DMPO as the radical trapping reagent of Er-CoP@NC/TM. (c) NH3 yield rates with and without 0.5 mol L-1 TBA. (d,e) Electrochemical in situ Raman spectra of Er-CoP@NC/TM. (f) Electrochemical in situ FTIR on the Er-CoP@NC/TM electrode in 0.1 mol L-1 KOH containing 0.1 mol L-1 NO2-.

Fig. 8. (a) Difference between the charge densities of CoP@NC/TM and Er-CoP@NC/TM, with purple indicating electron enrichment and blue indicating electron deficiency. (b) Free energy diagram for the NO2-RR on CoP@NC/TM and Er-CoP@NC/TM without applied potential at pH = 13 and T = 298 K. (c) Free energy diagram for the HER on different active metal sites of CoP@NC/TM and Er-CoP@NC/TM without applied potential at pH = 0 and T = 298 K.

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