Nanoporous Silver via Electrochemical Dealloying and Its Superior Detection Sensitivity to Formaldehyde

doi:10.11900/0412.1961.2019.00054

Acta Metall Sin

2019, Vol. 55

Issue (10): 1302-1310 DOI: 10.11900/0412.1961.2019.00054

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Nanoporous Silver via Electrochemical Dealloying and Its Superior Detection Sensitivity to Formaldehyde

YANG Yulin¹,MU Zhangyan¹,FAN Zheng¹,DAN Zhenhua^1,²(

),WANG Ying²,CHANG Hui¹

1. College of Materials Science and Engineering, Nanjing Tech University, Nanjing 210009, China
2. State Key Laboratory of Metal Material for Marine Equipment and Application, Anshan Iron and Steel Group Corporation, Anshan 114021, China

Cite this article:

YANG Yulin, MU Zhangyan, FAN Zheng, DAN Zhenhua, WANG Ying, CHANG Hui. Nanoporous Silver via Electrochemical Dealloying and Its Superior Detection Sensitivity to Formaldehyde. Acta Metall Sin, 2019, 55(10): 1302-1310.

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Abstract

Nanoporous silver (NPS) with high specific surface area has a great potential application in efficient formaldehyde detection. In this work, NPS was prepared by potentiostatic or galvanostatic electrochemical dealloying of Ag₃₀Zn₇₀ precursor alloys. The results reveal that applied potential or current has a significant influence on the composition, morphology and nanoporous structure of NPS. A bi-continuous NPS with an average pore size of 80 nm was obtained by electrochemical dealloying in 0.1 mol/L HCl solution at a constant current density of 2.5 mA/cm² for 6000 s. The cyclic voltammetry experiment results showed that NPS has a superior formaldehyde catalysis and detection abilities in 0.5 mol/L KOH solution due to the optimal combination of nanopores and Ag ligaments in nanoporous structure. The higher formaldehyde catalysis and detection abilities were exhibited at the NPS with smaller nanopores. The detection sensitivity of formaldehyde in NPS with the pore size of 80 nm was 0.22 mA·cm^-2·(mmol·L^-1)^-1 in the concentration range of 10~100 mmol/L, and the peak current density was 25.0 mA/cm² in 0.5 mol/L KOH solution with 100 mmol/L HCHO.

Key words: electrochemical dealloying nanoporous silver formaldehyde detection cyclic voltammetry

Received: 28 February 2019

ZTFLH:

TG146

Fund: Supported by National Defense Basic Scientific Research Program of China(JCKY08414C020);Top-Notch Academic Programs Project of Jiangsu Higher Education Institutions(PPZY2015B128);State Key Laboratory of Metal Material for Marine Equipment and Application(HG-SKL(2018)06)

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	Yulin YANG
	Zhangyan MU
	Zheng FAN
	Zhenhua DAN
	Ying WANG
	Hui CHANG

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https://www.ams.org.cn/EN/10.11900/0412.1961.2019.00054 OR https://www.ams.org.cn/EN/Y2019/V55/I10/1302

Fig.1 Transient changes of response current density of electrochemical dealloying of Ag₃₀Zn₇₀ alloy with different applied potentials in 0.1 mol/L HCl solution with 1 g/L PVP

Fig.2 XRD spectra of Ag₃₀Zn₇₀ original alloys and after electrochemical dealloying with different potentials in 0.1 mol/L HCl solution with 1 g/L PVP

Fig.3 Low (a, c, e, g) and high (b, d, f, h) magnified SEM images of Ag₃₀Zn₇₀ alloys after electrochemical dealloying with applied potentials of 0.10 V (a, b), 0.15 V (c, d), 0.20 V (e, f) and 0.30 V (g, h) in 0.1 mol/L HCl solution with 1 g/L PVP

Fig.4 Transient changes of potential of electrochemical dealloying of Ag₃₀Zn₇₀ alloy with different current densities in 0.1 mol/L HCl solution

Fig.5 XRD spectra of Ag₃₀Zn₇₀ alloys after electrochemical dealloying with different current densities in 0.1 mol/L HCl solution

Fig.6 Low (a, c) and high (b, d) magnified SEM iamges of Ag₃₀Zn₇₀ alloys after electrochemical dealloying with applied current densities of 2.5 mA/cm² (a, b) and 5.0 mA/cm² (c, d) in 0.1 mol/L HCl solution

Fig.7 Cyclic voltammetry (CV) curves (a) and local magnification (b) of nanoporous silver (NPS) and Ag₃₀Zn₇₀ original alloy in 0.5 mol/L KOH solution with 50 mmol/L HCHO (Scan rate V=50 mV/s)

Fig.8 CV curves of NPS-3 in 0.5 mol/L KOH solution with 50 mmol/L HCHO at different scan rates (a), and linear relationship between peak current density and the square root of scan rates (b)

Fig.9 CV curves of NPS-3 in 0.5 mol/L KOH solution with 50 mmol/L HCHO in different cycle number at V=50 mV/s (a), and relationship between peak current density and cycle number (b)

Fig.10 CV curves of NPS-2 (a) and NPS-3 (b) in 0.5 mol/L KOH solution with 10, 30, 50, 80 and 100 mmol/L HCHO at V=50 mV/s, linear relationship between peak current density and formaldehyde concentrations (c) (C_HCHO—HCHO concentration)

[1]	Xu C X, Xu X H, Su J X ,et al. Research on unsupported nanoporous gold catalyst for CO oxidation [J]. J. Catal., 2007, 252: 243
[2]	Zeis R, Lei T, Sieradzki K, et al. Catalytic reduction of oxygen and hydrogen peroxide by nanoporous gold [J]. J. Catal., 2008, 253: 132
[3]	Jin Y, Li R, Zhang T. Formation of nanoporous silver by dealloying Ca-Ag metallic glasses in water [J]. Intermetallics, 2015, 67: 166
[4]	Qiu H J, Xue L Y, Ji G L, et al. Enzyme-modified nanoporous gold-based electrochemical biosensors [J]. Biosens. Bioelectron., 2009, 24: 3014
[5]	Chen Y. The preparation and electrocatalytic properties of nanoporous silver [D]. Guilin: Guangxi Normal University, 2012
[5]	(陈颖. 纳米多孔银的制备及电催化性能研究 [D]. 桂林: 广西师范大学, 2012)
[6]	Li R, Liu X J, Wang H ,et al. Development of electrochemical supercapacitors with uniform nanoporous silver network [J]. Electrochim. Acta, 2015, 182: 224
[7]	Dan Z H, Qin F X, Sugawara Y, et al. Fabrication of nanoporous copper by dealloying amorphous binary Ti-Cu alloys in hydrofluoric acid solutions [J]. Intermetallics, 2012, 29: 14
[8]	Dan Z H, Qin F X, Yamaura S I ,et al. Refinement of nanoporous copper by dealloying MgCuY amorphous alloys in sulfuric acids containing polyvinylpyrrolidone [J].J. Electrochem. Soc., 2014, 161: C120
[9]	Qin F X, Dan Z H, Hara N ,et al. Selective dissolution of an amorphous Mg65Cu25Y10 alloy in organic acids and dilute HCl solution [J]. Mater. Chem. Phys., 2016, 179: 27
[10]	Dan Z H, Qin F X, Wada T, et al. Nanoporous palladium fabricated from an amorphous Pd42.5Cu30Ni7.5P20 precursor and its ethanol electro-oxidation performance [J]. Electrochim. Acta, 2013, 108: 512
[11]	Zhang C, Sun J Z, Xu J L ,et al. Formation and microstructure of nanoporous silver by dealloying rapidly solidified Zn-Ag alloys [J]. Electrochim. Acta, 2012, 63: 302
[12]	Forty A J, Durkin P. A micromorphological study of the dissolution of silver-gold alloys in nitric acid [J]. Philos. Mag., 1980, 42A: 295
[13]	Erlebacher J, Aziz M J, Karma A ,et al. Evolution of nanoporosity in dealloying [J]. Nature, 2001, 410: 450
[14]	Song T T, Gao Y L, Zhang Z H ,et al. Influence of magnetic field on dealloying of Al-25Ag alloy and formation of nanoporous Ag [J]. CrystEngComm, 2012, 14: 3694
[15]	Ji H, Wang X G, Zhao C C ,et al. Formation, control and functionalization of nanoporous silver through changing dealloying media and elemental doping [J]. CrystEngComm, 2011, 13: 2617
[16]	Zhang M, Junior A M J, Pang S J, et al. Fabrication of nanoporous silver with open pores [J]. Scr. Mater., 2015, 100: 21
[17]	Li Z Q, Wang X M, Lu X. Refinement of nanoporous silver by adding surfactant to the electrolyte [J]. ECS Electrochem. Lett., 2014, 3: C13
[18]	Cui Y L. Improving of the method of formaldehyde manual titration [J]. Chem. Eng. Des. Commun., 2014, 40(3): 51
[18]	(崔永乐. 手动滴定测定甲醛方法的改进 [J]. 化学设计通讯, 2014, 40(3): 51)
[19]	Yao J D, Sun D, Zhong C H, et al. Determination of formaldehyde content in soil by acetylacetone spectrophotometry [J]. Chem. Anal. Meterage, 2017, 26(1): 85
[19]	(姚洁丹, 孙丹, 钟灿红等. 乙酰丙酮分光光度法测定土壤中甲醛 [J]. 化学分析计量, 2017, 26(1): 85)
[20]	Gao M H, Zhou S L, Yang Z Y ,et al. Spectrophotometric determination of formaldehyde in water sample with amino acid-acetylacetone [J]. Phys. Test. Chem. Anal., 2014, 50B: 50
[20]	(高明慧, 周仕林, 杨卓圆等. 氨基酸-乙酰丙酮分光光度法测定水样中甲醛 [J]. 理化检验, 2014, 50B: 50)
[21]	Dai Z R, Lin M F, Zhang C X. Rapid detection of formaldehyde content in fresh milk by gas chromatography [J]. Food Res. Dev., 2015, 36(24): 154
[21]	(戴梓茹, 林美芳, 张晨晓. 气相色谱法快速测定鲜牛乳中的甲醛含量 [J]. 食品研究与开发, 2015, 36(24): 154)
[22]	Xu J L, Wang Y, Zhang Z H. Potential and concentration dependent electrochemical dealloying of Al2Au in sodium chloride solutions [J]. J. Phys. Chem., 2012, 116C: 5689
[23]	Zhang Q, Wang X G, Qi Z ,et al. A benign route to fabricate nanoporous gold through electrochemical dealloying of Al-Au alloys in a neutral solution [J]. Electrochim. Acta, 2009, 54: 6190
[24]	Fu C Q, Xu L J, Dan Z H, et al. Annealing effect of amorphous Fe-Si-B-P-Cu precursors on microstructural evolution and redox behavior of nanoporous counterparts [J]. J. Alloys Compd., 2017, 726: 810
[25]	Zhang Q, Zhang Z H. On the electrochemical dealloying of Al-based alloys in a NaCl aqueous solution [J]. Phys. Chem. Chem. Phys., 2010, 12: 1453
[26]	Dursun A, Pugh D V, Corcoran S G. Dealloying of Ag-Au alloys in halide-containing electrolytes: Affect on critical potential and pore size [J]. J. Electrochem. Soc., 2003, 150: B355
[27]	Yang C L, Xiang Y, Yang S C ,et al. Nanoporous gold by dealloying and its electrocatalytic oxidation abilities towards glucose [J]. Rare Met. Mater. Eng., 2014, 43: 230
[27]	(杨春雷, 项桦, 杨圣晨等. 纳米多孔金的制备及其对葡萄糖催化性能研究 [J]. 稀有金属材料与工程, 2014, 43: 230)
[28]	Sun Y, Ye J, Shan Z W ,et al. The mechanical behavior of nanoporous gold thin films [J]. JOM, 2007, 59(9): 54.
[29]	Bai L. Study on the electrocatalysis properties of nanoporous silver [D]. Dalian: Dalian Jiaotong University, 2015
[29]	(白璐. 多孔银的电催化性能研究[D]. 大连: 大连交通大学, 2015)
[30]	Zhao Y, Qin S J, Li Y ,et al. Electrodeposition of dendritic Pd nanoarchitectures on n-GaN(0001): Nucleation and electrocatalysis for direct formic acid fuel cells [J]. Electrochim. Acta, 2014, 145: 148
[31]	Duan D H, Liu H H, You X, et al. Anodic behavior of carbon supported Cu@Ag core-shell nanocatalysts in direct borohydride fuel cells [J]. J. Power Sources, 2015, 293: 292
[32]	Yu Y N, Jia M Z, Tian H F ,et al. The fabrication of silver ion implantation-modified electrode and its application in electrocatalytic oxidation of formaldehyde [J]. J. Power Sources, 2014, 267: 123

[1]	SONG Lixiao ZHANG Zhao ZHANG Jianqing CAO Chunan. ELECTROPLATING MECHANISM OF NANOSTRUCTURED BLACK Ni FILMS[J]. 金属学报, 2011, 47(1): 123-128.
[2]	SHI Jinjie SUN Wei GENG Guoqing. INFLUENCE OF CARBONATION ON THE CORROSION PERFORMANCE OF STEEL HRB335 IN SIMULATED CONCRETE PORE SOLUTION[J]. 金属学报, 2011, 47(1): 17-24.
[3]	;. EXPERIMENTAL RESEARCH OF PREPARATION OF CaB6 BY MOLTEN SALT ELECTROLYSIS METHOD[J]. 金属学报, 2008, 44(10): 1243-1246 .
[4]	YIN Renhe; ZHAO Yaping; DAI Yingchun; ZHANG Xinsheng. Effect of Sodium Salicylate on Electropolymerization of Pyrrole on Zincated Steel[J]. 金属学报, 2004, 40(2): 168-172 .
[5]	DU Senlin;SU Mingzhong;Changchun Institute of Applied Chemistry; Academia Sinica. ELECTROCHEMICAL BEHAVIOUR OF Nd~3+ REDUCED ON LIQUID Ga ELECTRODE IN MOLTEN CHLORIDE[J]. 金属学报, 1991, 27(3): 111-115.

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