Preparation of five-fold twinned copper nanowires@polypyrrole and their electrocatalytic conversion of nitrate to ammonia

doi:10.11949/0438-1157.20240007

Abstract

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 five-fold twinned copper nanowires@polypyrrole (T-CuNW@ppy) by hydrothermal coupled in-situ reduction method, which achieved ammonia production activity under low bias voltage, improved Faradaic efficiency, and significantly improved corrosion resistance. At a bias of -0.4 V (vs RHE), the T-CuNW-10 exhibited an impressive ammonia synthesis activity of 13.83 $m g · m g - 1 · h - 1$ ; while at a bias of -0.7 V (vs RHE) it reached 23.24 $m g · m g - 1 · h - 1$ . Furthermore, the Faradaic efficiency of $N O 2 -$ and NH₃ is a close to 100%. Additionally, the corrosion current is reduced to 3.14 μA·cm^-2. 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

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（可逆氢电极）时T-CuNW-10样品合成氨活性达到13.83 $m g · m g - 1 · h - 1$ ，偏压-0.7 V（可逆氢电极）时达到23.24 $m g · m g - 1 · h - 1$ ；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%；腐蚀电流降低至3.14 μA·cm^-2。最终实现催化剂高效稳定硝酸根还原制氨性能的提升，可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

CLC Number:

TQ 131.2

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, 2024, 75(4): 1519-1532.

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[J]. 化工学报, 2024, 75(4): 1519-1532.

Figures/Tables 11

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

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

Fig.2 XRD patterns of samples

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

Fig.4 TEM, Raman and XPS spectra of samples

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

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

催化剂	偏压(vs RHE)/V	NH₃产生速率	法拉第效率/%	文献
T-CuNW	-0.4	12.04 $m g · m g - 1 · h - 1$ (12.04 mg·cm^-2· h^-1)	84.1	本论文
T-CuNW@ppy	-0.4	13.83 $m g · m g - 1 · h - 1$ (13.83 mg·cm^-2· h^-1)	83.0	本论文
Cu₄₉Fe₁-NRA	-0.7	4.08 mg·cm^-2·h^-1	94.5	[32]
Cu SACs	-0.9	1.12 mg·cm^-2·h^-1	85.5	[33]
Cu₁Co₁HHTP	-0.6	5.09 mg·cm^-2·h^-1	96.4	[34]
Cu-Fe₂O₃	-0.6	179.55 $m g · m g - 1 · h - 1$	约100	[35]
Cu Ni NPS/CF	-0.48	94.57 mg· cm^-2·h^-1	97.0	[36]
T40-CuNCs	-0.6	2.62 mg·cm^-2·h^-1	96.8	[37]
Cu SCCs	-0.5	1.99 mg·cm^-2·h^-1	96.0	[38]
Cu-HTBs	-0.7	23789.8 $m g · m g - 1 · h - 1$	90.0	[39]
Cu₅Pd NCs	-0.7	32 mg·cm^-2·h^-1	95.5	[40]
Ru_0.15Cu_0.85	-0.2	26.25 $μ g · m g - 1 · h - 1$	4.4	[41]

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

催化剂	偏压(vs RHE)/V	NH₃产生速率	法拉第效率/%	文献
T-CuNW	-0.4	12.04 $m g · m g - 1 · h - 1$ (12.04 mg·cm^-2· h^-1)	84.1	本论文
T-CuNW@ppy	-0.4	13.83 $m g · m g - 1 · h - 1$ (13.83 mg·cm^-2· h^-1)	83.0	本论文
Cu₄₉Fe₁-NRA	-0.7	4.08 mg·cm^-2·h^-1	94.5	[32]
Cu SACs	-0.9	1.12 mg·cm^-2·h^-1	85.5	[33]
Cu₁Co₁HHTP	-0.6	5.09 mg·cm^-2·h^-1	96.4	[34]
Cu-Fe₂O₃	-0.6	179.55 $m g · m g - 1 · h - 1$	约100	[35]
Cu Ni NPS/CF	-0.48	94.57 mg· cm^-2·h^-1	97.0	[36]
T40-CuNCs	-0.6	2.62 mg·cm^-2·h^-1	96.8	[37]
Cu SCCs	-0.5	1.99 mg·cm^-2·h^-1	96.0	[38]
Cu-HTBs	-0.7	23789.8 $m g · m g - 1 · h - 1$	90.0	[39]
Cu₅Pd NCs	-0.7	32 mg·cm^-2·h^-1	95.5	[40]
Ru_0.15Cu_0.85	-0.2	26.25 $μ g · m g - 1 · h - 1$	4.4	[41]

Fig.6 (a) Cycling tests of T-CuNW-10 for eNITRR tests at -0.4 V（vs RHE）; (b) Time dependent concentration change of NO3-, NO2- and NH3 over T-CuNW-10 at -0.4 V（vs RHE）; (c) Time dependent concentration change of FE; (d) Time dependent concentration change of total nitrogen at -0.4 V（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

Fig.7 (a) Open circuit potentials decays with rest time; (b) Polarization curves; (c),(d) Curve of Tafel; (e)，(f)Contact angle measurements; (g) Nyquist plots for the as-synthesized samples; (h)，（i） Cyclic voltammograms; (j) Linear regression curve of difference in current density and scanning rate

Table 3 Tafel curve fitting values of T-CUNW-10 and T-CuNW catalysts in 1 mol·L-1 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

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

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