五重孪晶铜纳米线@聚吡咯制备及其电催化硝酸盐还原制氨研究

doi:10.11949/0438-1157.20240007

摘要/Abstract

摘要：

合理设计高活性、高选择性、高稳定性、低成本纳米结构催化剂，是电催化硝酸根还原制氨的一个重大挑战。采用水热法耦合原位还原法制备了厚度可控的聚吡咯包裹五重孪晶铜纳米线催化剂，实现了低偏压下产氨活性、法拉第效率的提高以及对抗腐蚀能力的大幅提升。偏压为-0.4 V（标准氢电极）时T-CuNW-10样品合成氨活性达到13.83 mg·mg_cat.^-1 h^-1，偏压-0.7 V（标准氢电极）时达到23.24 mg·mg_cat.^-1 h^-1；中间产物亚硝酸根与产物氨二者加和的法拉第效率（FE）接近100%；腐蚀电流降低了6.7倍。最终实现催化剂高效稳定硝酸根还原制氨性能的提升，为开发设计工业应用催化剂提供思路参考。

关键词: 聚吡咯, 五重孪晶铜, 纳米材料, 硝酸根, 电化学合成氨, 催化剂

Abstract:

Reasonable design of nanostructured catalysts with high activity, selectivity, stability, and low cost is a significant challenge for achieving efficient electrocatalytic reduction of nitrate to ammonia. In this study, we successfully prepared a copper@polypyrrole coaxial nanowires (T-CuNW@ppy) by hydrothermal coupled in-situ reduction method. Remarkably, the NH₃production activity, Faraday efficiency, and corrosion resistance were greatly enhanced under low bias pressure conditions. At a bias of -0.4V vs.RHE, the T-CuNW-10 exhibited an impressive ammonia synthesis activity of 13.83 mg·mg_cat.^-1 h^-1; while at a bias of -0.7V vs.RHE it reached 23.24 mg·mg_cat.^-1 h^-1. Furthermore, the Faraday efficiency of NO₂^- and NH₃ is a close to 100%. Additionally, the corrosion current was reduced by 6.7 times compared to previous catalysts studied in this field. Overall, our findings demonstrate that this catalyst not only exhibits high efficiency and stability in nitrate reduction performance but also provides valuable insights for the development and design of industrial application-oriented catalysts.

Key words: polypyrrole, five-fold twinned copper, nanomaterials, nitric acid, electrochemical ammonia synthesis, catalyst

中图分类号:

TQ 131.2

严孝清, 赵瑛, 张宇哲, 欧鸿辉, 黄起中, 胡华贵, 杨贵东. 五重孪晶铜纳米线@聚吡咯制备及其电催化硝酸盐还原制氨研究[J]. 化工学报, DOI: 10.11949/0438-1157.20240007.

Xiaoqing YAN, Ying ZHAO, Yuzhe ZHANG, Honghui OU, Qizhong HUANG, Huagui HU, Guidong YANG. Preparation of five-fold twinned copper nanowires @ polypyrrole and their electrocatalytic conversion of nitrate to ammonia[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240007.

图/表 11

表1 T-CuNW@ppy催化剂的制备参数表

Table 1 Preparation parameters of T-CuNW@ppy

样品编号	T-CuNW（mg）	吡咯（μL）	过硫酸铵（mg）	碳酸氢钠（mg）
T-CuNW	50	0	0	0
T-CuNW-5	50	5	0.0114	0.0084
T-CuNW-10	50	10	0.0228	0.0168
T-CuNW-20	50	20	0.0456	0.0336

图1 T-CuNW@ppy样品制备示意图

Fig. 1 Schematic diagram of the synthesis of T-CuNW@ppy

图2 样品XRD谱图

Fig. 2 XRD spectra of samples

图3 T-CuNW和T-CuNW@ppy系列样品SEM图(a-d)；T-CuNW-10样品的HAADF-STEM图(e)和EDS图(f-h)

Fig. 3 SEM images of T-CuNW and T-CuNW@ppy samples(a-d); HAADF-STEM diagram (e) and EDS diagram (f-h) of T-CuNW-10 sample

图4 样品的TEM图、拉曼光谱图及XPS谱图

Fig. 4 TEM, Raman and XPS spectra of samples

图5 T-CuNW@ppy系列样品在(a) 1 M KOH电解液和(b)1 M KOH+0.1 M KNO3电解液中的LSV曲线；不同电压下系列样品在1 M KOH+0.1 M KNO3溶液中的i-t曲线：(c)T-CuNW，(d)T-CuNW-5，(e)T-CuNW-10和(f)T-CuNW-20；不同电压下T-CuNW、ppy和T-CuNW@ppy系列样品在1 M KOH+0.1 M KNO3溶液中的(g)NH3产品活性和(h)NH3的法拉第效率; (i)T-CuNW-10分别于在-0.4 V vs.RHE下1 M KOH（有0.1 M KNO3）溶液中，在-0.4 V vs.RHE下1 M KOH（无0.1 M KNO3）溶液和无施加偏压下1 M KOH（有0.1 M KNO3）溶液中的NH3产量

Fig. 5 The LSV polarization curves of the as-synthesized samples in electrolytes using 0.1 M KOH as the solvent without (a) and with (b) adding 0.1 M NO3-. I-t curves of the as-synthesized samples: (c)T-CuNW, (d)T-CuNW-5, (e)T-CuNW-10 and (f)T-CuNW-20. (g) eNITRR performance of the as-synthesized samples under different potential in 1M KOH with 0.1M KNO3 (h) FE of the as-synthesized samples under different potential in 1M KOH with 0.1M KNO3. (i) the eNITRR performance of T-CuNW-10 in electrolytes using 0.1 M KOH as the solvent without and with adding 0.1 M NO3-

表2 T-CuNW、T-CuNW@ppy与其他典型材料的硝酸根还原制氨活性比较

Table 2 Comparison of the eNITRR performance of T-CuNW， T-CuNW@ppy， and other typical materials

时间	催化剂	偏压 (vs.RHE)	产氨速率	法拉第效率	期刊	参考文献
	T-CuNW	-0.4 V	12.04 mg·mg_cat.^-1 h^-1 (12.04 mg·cm^-2· h^-1)	84.1%	本论文催化剂
	T-CuNW@ppy	-0.4 V	13.83 mg·mg_cat.^-1 h^-1 (13.83 mg·cm^-2· h^-1)	83.0%	本论文催化剂
2021	Cu₄₉Fe₁-NRA	-0.7 V	4.08 mg·cm^-2·h^-1	94.5%	ChemCatChem	32
2022	Cu SACs	-0. 9 V	1.12 mg·cm^-2·h^-1	85.5%	ACS Catalysis	33
2022	Cu₁Co₁HHTP	-0.6 V	5.09 mg·cm^-2·h^-1	96.4%	Angewandte Chemie-International Edition	34
2022	Cu-Fe₂O₃	-0.6 V	179.55 mg·mg_cat.^-1 h^-1	≈100%	Nature communications	35
2023	Cu Ni NPS/CF	-0.48 V	94.57 mg· cm^-2·h^-1	97.0%	Small	36
2023	T40-CuNCs	-0.6 V	2.62 mg·cm^-2·h^-1	96.8%	ACS Applied Materials &Interfaces	37
2023	Cu SCCs	-0.5 V	1.99 mg·cm^-2·h^-1	96.0%	Nano Research	38
2023	Cu-HTBs	-0.7 V	23789.8 mg·mg^-1_cat·h^-1	90.0%	Advanced Materials	39
2023	Cu₅Pd NCs	-0.7 V	32 mg·cm^-2·h^-1	95.5%	ChemCatChem	40
2023	Ru_0.15Cu_0.85	-0.2 V	26.25 μg·mg^-1_cat·h^-1	4.4%	ACS Applied Materials &Interfaces	41

图6 （a）T-CuNW-10在-0.4V vs.RHE下含有0.1 M NO3-的1 M KOH电解质中的15次循环测试的NH3 产品活性和NH3的法拉第效率; T-CuNW-10在-0.4V vs.RHE下，1 M KOH+0.1 M KNO3电解质中（b）反应物NO3--N、产物NO2--N、NH3-N浓度和NH3的法拉第效率随时间的变化规律和（c）NH3和NO2-法拉第效率随时间的变化规律;（d）T-CuNW-10在-0.4V vs.RHE下，1 M KOH+0.1 M KNO3电解质中检测的总氮浓度随时间的变化规律; T-CuNW在-0.4V vs. RHE下含有不同初始浓度NO3-的1 M KOH电解质中的（e）NH3产率和NH3法拉第效率；（f）NH3和NO2-法拉第效率随初始NO3-浓度的变化规律

Fig. 6 (a) the cycling tests of T-CuNW-10 for eNITRR tests at-0.4V vs.RHE. (b) Time dependent concentration change of NO3-, NO2- and NH3 over T-CuNW-10 at-0.4V vs.RHE. (c) Time dependent concentration change of FE. (d) Time dependent concentration change of total nitrogen at-0.4V vs.RHE. (e) NH3 yield rate and FE of T-CuNW-10 with different concentrations of nitrate. (f) FE of NH3 and NO2- on T-CuNW-10 with different concentrations of nitrate

表3 T-CuNW-10和T-CuNW催化剂在1 M KOH溶液中的Tafel曲线拟合值

Table 3 Tafel curve fitting values of T-CUNW-10 and T-CuNW catalysts in 1 M KOH solution

样品名称	E_corr (mV)	i_corr (μA·cm^-2)
T-CuNW	-416.90	21.01
T-CuNW-10	-137.98	3.14

表4 T-CuNW-10的ECSA分析结果及与T-CuNW的对比

Table 4 ECSA test of T-CUNW-10 and T-CuNW

样品名称	C_dl （mF·cm^-2）	ECSA（cm²）
T-CuNW	2.56	64
T-CuNW-10	8	200

图7 （a）T-CuNW-10和T-CuNW催化剂在1 M KOH溶液中的开路电位-时间曲线；（b）T-CuNW-10和T-CuNW催化剂在1 MKOH溶液中的极化曲线；（c）T-CuNW和（d）T-CuNW-10催化剂在1 M KOH溶液中的Tafel拟合曲线;（e）T-CuNW和（f）T-CuNW-10两种催化剂疏水性测试;（g）T-CuNW-10和T-CuNW催化剂在1 M Na2SO4溶液中的电化学阻抗谱图；T-CuNW-10样品在不同扫描速率下的（h）循环伏安曲线图（CV）和（i）电流密度差与扫描速率的线性拟合曲线图的线性拟合曲线

Fig. 7 (a) Open circuit potentials decays with rest time. (b) polarization curves. (c,d) the curve of Tafel. (e-f) contact angle measurements of T-CuNW and T-CuNW-10. (g) nyquist plots for the as-synthesized samples. (h) cyclic voltammograms. (i) The linear regression curve of the difference in current density and scanning rate

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