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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

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Front. Chem. Sci. Eng.    2017, Vol. 11 Issue (3) : 448-464    https://doi.org/10.1007/s11705-017-1611-9
REVIEW ARTICLE
Recent advances in SERS detection of perchlorate
Jumin Hao1,2, Xiaoguang Meng1()
1. Center for Environmental Systems, Stevens Institute of Technology, 1 Castle Point Terrace, Hoboken, NJ 07030, USA
2. NovelTech JMC Inc., 409 Minnisink Road Suite 208, Totowa, NJ 07512, USA
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Abstract

Perchlorate has recently emerged as a widespread environmental contaminant of healthy concern. Development of novel detection methods for perchlorate with the potential for field use has been an urgent need. The investigation has shown that surface-enhanced Raman scattering (SERS) technique has great potential to become a practical analysis tool for the rapid screening and routine monitoring of perchlorate in the field, particularly when coupled with portable/handheld Raman spectrometers. In this review article, we summarize progress made in SERS analysis of perchlorate in water and other media with an emphasis on the development of SERS substrates for perchlorate detection. The potential of this technique for fast screening and field testing of perchlorate-contaminated environmental samples is discussed. The challenges and possible solutions are also addressed, aiming to provide a better understanding on the development directions in the research field.
Keywords perchlorate      SERS      detection      substrate      modification      nanostructure     
Corresponding Author(s): Xiaoguang Meng   
Online First Date: 09 January 2017    Issue Date: 23 August 2017
 Cite this article:   
Jumin Hao,Xiaoguang Meng. Recent advances in SERS detection of perchlorate[J]. Front. Chem. Sci. Eng., 2017, 11(3): 448-464.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-017-1611-9
https://academic.hep.com.cn/fcse/EN/Y2017/V11/I3/448
Fig.1  Schematic of SERS phenomenon for an analyte on AuNPs [33]. Reproduced with permission from The Royal Society of Chemistry
Fig.2  Scheme 1&chsp;?Illustratration of the types and fabrication routes of the significant SERS substrates used for perchlorate SERS detection, as well as the sampling methods for water samples prior to SERS measurements corresponding to the substrates types. It also shows the advantages and disadvantages for convenient comparison among them
Fig.3  Typical SERS spectra of (a) AgNPs/Cu nanofilm (background), (b) ClO4− at 104ppb on AgNPs/Cu nanofilm, and (c) normal Raman spectrum of 107ppb perchlorate aqueous solution [22]. Adapted with permission from Elsevier B.V.
SERS substrate Modification reagent and cationic group Sampling method Laser
l /nm		 SERS peak /cm −1 LOD /ppb Ref.
Roughened Ag electrode Various cationic thiols:
–NH3+, –NH+ (CH3)2, etc.		 Flow Cell 785 935 5000 a) [ 18]
AgNPs
(colloid)		 No modification Mix-Drop-Dry 785 941 500 [ 19]
AuNPs
(colloid)		 Cystamine dihydrochloride (CYD): –NH 3+ Mix-Drop-Dry 785 929–931 500 [ 20]
AuNPs/SiO 2
(colloid)		 Various silane reagents:
–NH3+, –NH+ (CH3)2, etc.		 Mix-Drop-Dry 785 929–931 100 [ 13]
AuNPs
(colloid)		 2-Dimethylaminoethanethiol hydrochloride (DMAH):
–NH+ (CH3)2 		Mix-Drop-Dry 785 934 0.1 [ 14]
AuNPs
(colloid)		 Poly(diallyldimethylammonium chloride) (PDDA):>N + (CH3)2 Mix-Drop-Dry 785 931 25 [ 25]
AgNPs/Glass or AgNPs/Capillary
(solid)		 Various silane reagents:
–NH3+, –NH+ (CH3)2, etc.		 Drop b)
Flow Cell c) 		785 930–932 100 b)300 c) [ 9]
AgNPs/Glass
(solid)		 Branched polyethyleneimine
(BPEI): –NH3+ 		Drop 532 928 8 [ 21]
AgNPs/Cu foil
(solid)		 No modification Drop-Dry 780 930 50 [ 22]
AgNPs/rCu foil
(solid)		 Cysteamine hydrochloride (CYH): –NH 3+ Drop 780 930 5
1000 d) 		[ 23, 24]
AgNPs/Fe 3O4/Support/Megnet (solid) 2-Dimethylaminoethanethiol hydrochloride (DMAH):
–NH+ (CH3)2 		Flow Cell 785 923 5000 a) [ 15]
Ag nanoplate/Cu wire
(solid)		 Sodium diethyldithiocarb- amate (DDTC): =N + (C2H5) Dip 785 932 6 e)
81f) 		[ 27]
AgNRs/Si wafer
(solid)		 No modification Transfer-Drop-Dry 785 934 N/A g) [ 28]
Tab.1  Summary of significant advances in the perchlorate SERS detection reported in the literature
Fig.4  Illustration of the interactions between perchlorate and protonated or deprotonated cystamine-modified gold nanoparticles under both acidic and alkaline pH conditions [20]. Reproduced with permission from Elsevier B.V.
Fig.5  (a) SERS detection of ClO4− at various concentrations using CYD-modified AuNPs at pH 2; (b) ClO4− peak intensity at ~930 cm−1as a function of the concentration [20]. Reproduced with permission from Elsevier B.V.
Fig.6  SEM image of adsorbed AuNPs on SiO2 nanospheres modified mixed –N+(CH3)3 and –NH2. The scale at the bottom 1 μm [13]. Reproduced with permission from Elsevier B.V.
Fig.7  (a) Photo of the flow cell used to evaluate the SERS response of capture matrices (DMAH-modified AgNPs/Fe3O4magnetic microparticles) to perchlorate. Top-left inset shows a schematic illustration of a DMAH-modified AgNPs/Fe3O4magnetic microparticle and the capture of perchlorate ion; Top-right inset shows SERS spectra obtained in the flow cell system; (b) schematics of the flow cell showing the structure [15]. Adapted with permission from Elsevier B.V.
Fig.8  (a) SERS spectra of ClO4−on the DMAH-modified AgNPs/Fe3O4capture matrices in the flow cell measured as a function of total volume of 5 ppm perchlorate solution flowing through the cell at a constant rate; (b) plot of perchlorate peak area as a function of volume of 5 ppm perchlorate solution. The mass quantity of perchlorate that flowed over the capture matrices is indicated [15]. Adapted with permission from Elsevier B.V.
Fig.9  Schematic illustration of preparation of the SERS substrate CYH-AgNF/rCu by a galvanic replacement reaction followed by CYH modification [23]. Reproduced with permission from Elsevier B.V.
Fig.10  SERS spectra of (a) the regenerated CYH-AgNF/rCu substrates and (b) 3 ppm perchlorate solutions on the regenerated substrates at different regeneration cycles (from bottom to up) of 1, 2, 4, 7, and 10 cycles [23]. Reproduced with permission from Elsevier B.V.
Fig.11  (a) The FE-SEM image of the fabricated SERS substrate. SERS spectra of (b) the water-dissolved explosives, after the oil-, organic-, and wax-based extraction with pentane, and (c) the water-dissolved explosives, after burned in the open flame [28]. Addopted with permission from Elsevier B.V.
Fig.12  Schematic of the process of microextraction and determination of perchlorate using DDTC-modified Ag/Cu fiber [27]. Reproduced with permission from The Royal Society of Chemistry
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