Over the years, intensive research works have been devoted to conducting polymers due to their potential application in many fields such as fuel cell, sensors, and capacitors. To improve the properties of these compounds, several new approaches have been developed which consist in combining conducting polymers and nanoparticles. Then, this review intends to give a clear overview on nanocomposites based on conducting polymers, synthesis, characterization, and their application as electro- chemical sensors. For this, the paper is divided into two parts: the first part will highlight the nanocomposites synthesized by combination of carbon nanomaterials (CNMs) and conducting polymers. The preparation of polymer/CNMs such as graphene and carbon nanotube modified electrode is presented coupled with relevant applications. The second part consists of a review of nanocomposites synthesized by combination of metal nanoparticles and conducting polymers. Keywords Conducting polymers · Carbon nanomaterials · Metal nanoparticles · Nanocomposites AbbreviationsCNFs Carbon nanofibers 1H NMR 1H nuclear magnetic reso-CNMs Carbon nanomaterials nance spectrometerCNs Carbon nanospheres 3D-RGO Three-dimensional reduced CNTs Carbon nanotubes graphene oxideCPs Conducting polymers AA Ascorbic acid CPE Carbon paste electrode AFM Atomic force microscope CRGO Chemically reduced graphene AgNPs Silver nanoparticles oxide AgNWs Silver nanowiresCTAB Cetyltrimethylammonium AgαCRP C-reactive protein bromide ANI AnilineCuNPs Copper nanoparticles ATP AttapulgiteCuS Copper sulfide AuNPs Gold nanoparticlesCV Cyclic voltammetry BET Brunauer–Emmett–TellerDA Dopamine C-CNTs Crosslinked carbon nanotubesDAN Diaminonaphthalene DMF N,N-Dimethylformamide DMFCs Direct methanol fuel cells * Mama El Rhazi DMSO Dimethyl sulfoxide firstname.lastname@example.org EDOT 3,4-Ethylenedioxythiophene EHDA Electrohydrodynamic Laboratory of Materials, Membranes and Environment, EIS Electrochemical impedance Faculty of Sciences and Technologies of Mohammedia, University Hassan II of Casablanca, BP 146, spectroscopy 20800 Mohammedia, Morocco f-MWCNTs Functionalized MWCNT Laboratory of Materials Engineering for the Environment FTIR Fourier-transform infrared and Valorization, Faculty of Sciences Aïn Chock, BP 5366, GR Graphene Maârif, Casablanca, Morocco GaN Gallium nitride University of Dayton, 300 College Park, Dayton, OH 45469, GCE Glassy carbon electrode USA Vol.:(0123456789) 1 3 80 International Nano Letters (2018) 8:79–99 GO Graphene oxideSEM Scanning electron ITO Indium tin oxide microscopy LOD Limit of detectionSMZ Herbicide simazine LOQ Limit of quantificationSWCNT Single-walled carbon MIP Molecularly imprinted nanotubes polymer SWV Square wave voltammetry MIPM Molecularly imprinted poly-TEM Transmission electron mer membranes microscopy MnO-NPs Manganesedioxide TGA Thermal gravimetric analysis nanoparticlesXPS X-ray photoelectron MNPs Metal nanoparticles spectroscopy MoS Molybdenum disulfide YADH Alcohol dehydrogenase nanosheets MWCNT Multi-walled carbon nanotubes Introduction MWNTsg-PtBMA-b-PS Multiwall carbon nanotube graft polystyrene-block- Organic conducting polymers, born in 1977 with the pio- poly(tert-butyl methacrylate) neering work of MacDiarmid, have received great attention NiPs Nickel ion particles due to their potential application [1, 2]. Intensive research NPs Nanoparticles works have been devoted to preparation and characteriza- p-AHNSA Poly4-amino-3-hydroxy- tion of conducting polymers such as polyaniline (PANI), 1-naphthalene sulfonic acid polypyrrole (PPy), diaminonaphthalene (DAN), and their PANI Polyaniline derivatives. Their application in batteries, sensors, capaci- PdNPs Palladium nanoparticles tors, electronic devices, or electrochromic displays was very PEDOT Poly(3,4-ethylenedioxythio- promising [3–5]. Carbon nanomaterials (CNMs) including phene) fullerenes, single-walled carbon nanotubes (SWCNT), multi- PEDOT:PSS Poly(3,4-ethylenedioxythio- walled carbon nanotubes (MWCNT), carbon nanofibers phene)–polystyrene sulfonic (CNFs), carbon nanospheres (CNs), graphene, and graphene acid oxide (GO) are novel materials of the twenty-first century PNPAg Nanocomposite blend  because of their large surface area, good environmental Poly(DTCPA-co-BHTBT) Poly((2,5-dithie- stability , exceptional electrical, thermal, chemical, and nyl-3,4-(1,8-naphthalene) mechanical properties . Due to these properties, CNMs cyclopentadienone)-co- had found a great interest in fields of composite materials 4,7-bis(3-hexylthiophen-2-yl) and energy conversion , sensors , medicine , benzo [c] [1,2,5] thiadiazole emission devices , and nanoscale electronic components PPy Polypyrrole . PPyox Overoxidized polypyrrole Many efforts have been made to combine CNMs and PS Polystyrene polymers to produce functional nanocomposite materials PS-b-PtBMA Polystyrene-block-poly(tert- with superior properties for fundamental and technological butyl methacrylate) perspectives . The conducting polymers such as poly- PSS Poly(sodium aniline (PANI), polypyrrole (PPy), polythiophene (PTh), 4-styrenesulfonate) and poly(3,4-ethylenedioxythiophene) (PEDOT) have been PTh Polythiophene explored as matrices to incorporate a number of CNMs PtNPs Platinum nanoparticles such as: fullerenes , single and multi-walled carbon PVA Polyvinyl alcohol nanotubes (CNTs) [15, 16], carbon nanofibers (CNFs) PVP Polyvinylpyrrolydone [17, 18], carbon nanospheres (CNs) [19, 20], graphene, RGO Reduced graphene oxide and graphene oxide [21–23]. The incorporation of carbon RGO-g-PANI Polyaniline grafted reduced nanomaterials in polymer matrices is a very attractive way graphene oxide to combine the mechanical and electrical properties . SDBS Sodium dodecylbenzene These new nanocomposites open up new opportunities, sulfonate ranging from sensors [25–27], electrochemical capacitor SEBS Poly(styrene-b-(ethylene-co- [28, 29], solar cells , transistors , to molecular butylene)-b-styrene) electronic devices , etc. More recently, nanocomposite 1 3 International Nano Letters (2018) 8:79–99 81 based on CPs, and metal nanoparticles (MNPs) such as Nanocomposites synthesized gold, platinum, palladium, and silver with different com- by combination of carbon nanomaterials positions and dimensions have been intensively investi- and conducting polymers gated [32–36]. The incorporation of metal nanoparticles in polymers matrices would to a host nanocomposite with Combination of conducting polymer matrix and carbon additional physical properties [37–39]. Several approaches nanomaterials (CNMs) such as graphene, carbon nanofib- have been described and employed to synthesize metal ers (CNFs), and carbon nanotubes (CNTs) to form polymer or metal oxide nanoparticle-conducting polymers nano- nanocomposites plays a very promising role due to their composites [34, 38, 40]. Different approaches using elec- better structural and functional properties such as high trochemical methods involving incorporation of metal aspect ratio, high mechanical strength, and high electrical nanoparticles during the electrosynthesis of the polymer, properties [24, 47, 48]. In the last decade, large progress electrodeposition of metal nanoparticles on the preformed was made, resulting in the opening of new possibilities in polymer electrodes, reduction of metal salts dissolved in the use of these properties for a variety of applications. a polymer matrix or incorporation of preformed nano- The overall performances of CNMs/polymer nanocompos- particles during polymerization of monomers have been ites are largely governed by the dispersion of CNM in the reported. Chemical preparation , sonochemical method polymer matrix. Therefore, a homogeneous dispersion of , sol–gel technique , ultrasonic irradiation , CNM is an important issue in the preparation of CNM/ and photochemical preparation  have also been used. polymer nanocomposites [17, 22, 49–51]. Up to date, a Nanocomposites based on conducting polymers and nano- large number of reviews have been reported on compos- particles (CNMs or MNPs) were the focus of increasing ites of conducting polymers and CNMs for application numbers of papers or reviews to understand fundamental in supercapacitors and chemical sensors [52–54]. Carbon aspects and the potential applications of these nanostruc- nanotubes and graphene are considered as the most inno- tures . According to the sciences direct web site, the vative CNMs who are attracting enormous interest for number of paper devoted to nanocomposites based CP and their use in sensors  and their potential application as NPs increased from 3427 in 2011 to 7444 in July 2017, as energy storage materials . The most commonly used shown in Fig. 1, indicating the importance of nanomate- conducting polymers are polyaniline (PANI), polypyrrole rial composites. (PPy), and poly[3,4-ethylenedioxythiophene] (PEDOT) The present review analyzes the recent progresses in [56–58]. Several methods for synthesis of nanocompos- the synthesis of nanocomposites based on conducting ites have been reported in the literature. CNM/polymer polymers and carbon nanomaterials and/or metal nano- nanocomposites can be synthesized by electrochemical particles during the last years and their applications in the or chemical processing. Chemical method is the common field of electrochemical sensors. It should be noted that processing that can be performed either by solution mixing only conducting polymers with conjugated-π-bond will be or by in situ chemical polymerization. Solution mixing is considered in this review. the method in which CNMs and polymer are mixed with a suitable solvent, and then, the nanocomposites are formed after the evaporation of the solvent in a controlled condi- tion. It was demonstrated that this method enables to drop- cast films with up to 60 wt% CNT content, although can result in reagglomeration of the CNTs during the casting/ evaporation process . In situ chemical polymerization achieved by oxidation of corresponding monomers using an oxidizing agent. The main advantage of this method is that it produces polymer grafted CNMs, mixed with free polymer chains. Moreover, due to the small size of monomeric molecules, the homogeneity of the result- ing composite adducts is much higher than mixing CNTs and polymer chains in solution . However, it cannot achieve the same level of homogeneity and integrity in its polymerized product as can be produced by electrochemi- cal polymerization . The electrochemical polymeriza- tion takes only some minutes instead of some hours in case Fig. 1 Histogram representing the numbers of scientific articles pub- of chemical polymerization. Polymers can be formed by lished per year during the last 6 years (research performed on 10 July 2017 with “Science Direct”, with CP and NPs) 1 3 82 International Nano Letters (2018) 8:79–99 electrochemical deposition on electrodes modified with in solution form can be casted on suitable substrate or CNMs which leads to the better dispersion and interac- precipitated by filtration before being dried. tions between CNMs and polymer. Better uniformity can be obtained by the electrochemically co-deposited com- Electrochemical methods are investigated to prepare posites from a solution containing monomers and dis- CNM/polymer nanocomposites and are summarized in persed CNMs leading to the most homogeneous network Fig. 3. Two methods are generally used: structure. Figure 2 shows the schematic illustration of the process of fabricating CNM/polymer nanocomposites with (a) The modified electrode was prepared by dropping of traditional chemical methods. the well-dispersed carbon nanomaterials on the sur- face of the electrode substrate. Conducting polymers (a) Nanocomposites were prepared by in situ chemical were electropolymerized using cyclic voltammetry in polymerization involving monomer and carbon nano- the presence of monomer dissolved in a solution gener- materials with different weight ratios after being soni- ally in acidic medium [63, 64]. A typical example in cated to obtain homogenous mixture [60, 61]. Fig. 4 was obtained in our laboratory using this method (b) In mixing method, the commercial polymers were and concern polymerization of 1,5-diaminonaphthalene dissolved in suitable organic solvents, mixed and with CNFs . sonicated. Mangu et al. used N,N-dimethylforma- (b) Electrochemical co-deposition was performed in aque- mide (DMF), dimethyl sulfoxide (DMSO) to dissolve ous solution containing monomer and carbon nanoma- PEDOT:PSS in the volume ratio of 3:1 and 2-propanol, terials, using potentiostatic, galvanostatic, or cyclic ethylene glycol, DMSO, and DMF to dissolve PANI voltammetry (CV). The solution was stirred and ultra- . Then, carbon nanomaterials were added to this sonicated before polymerization. After electropolymer- solution and sonicated. These nanocomposites obtained ization, the modified electrode was washed thoroughly with water and dried at room temperature [66–68]. Fig. 2 Schematic illustration of chemical preparation method of CNMs/conducting polymer nanocomposites: a in-situ chemical polymerization of monomer and carbon nanoparticles, b sonication of commercial polymer solution and carbon nanoparticles 1 3 International Nano Letters (2018) 8:79–99 83 Fig. 3 Schematic illustration of electrochemical process of elaboration of CNMs/conducting polymer nanocomposites −1 Fig. 4 a Cyclic voltammograms of electropolymerization of 1,5-DAN 1,5-DAN, 50 mV s , b compared voltammograms between CPE/ at the surface of CPE/CNF during 40 consecutive potential cycles poly(1,5-DAN) and CPE/CNF/poly(1,5-DAN) at the 40th cycle  between − 0.2 and 1.0 V in a 1.0 M HCl solution containing 5 mM 1 3 84 International Nano Letters (2018) 8:79–99 The properties of these nanocomposites are also related MWCNT–PANI composite sensor synthesized was observed to the percentage of CNMs. The percentage of CNM plays to show superior sensitivities and excellent reversibility to an important role on the mechanical and electrical proper- 100 ppm of NO gas . Later, Sharma et al. studied the ties of nanocomposites and was studied by different authors. thermal properties of the MWCNT-conducting polymer The influence of the percentage of CNT in CNT/PANI com- composite. They utilized MWCNT with PEDOT:PSS and posite was investigated by Liu et al., increasing the mass PANI to develop high-temperature tolerant ammonia gas ratio of CNT to aniline, the diameter of core–shell poly- sensor. MWCNT–PEDOT:PSS composite was found to mer decreased, and therefore, the composite conductivity show better thermal stability than MWCNT–PANI com- decreased also. Less than 10% by weight, the composite posite. The MWCNT–PEDOT:PSS composite sensor was CNT/PANI showed a gradually increasing conductivity found to exhibit excellent response for trace level sensing . Gui et al. developed three PANI/graphene oxide (GO) (1–50 ppm) of ammonia gas than MWCNT–PANI compos- nanocomposite electrode materials from aniline (ANI) and ite . Pure carbon nanotubes (CNTs) were also used to GO by chemical polymerization with the mass ratio (ANI/ prepare PEDOT conducting polymer nanocomposite. Elec- GO) 1000:1, 100:1, and 10:1. The PANI/GO composite syn- trochemical polymerization of PEDOT/CNT nanocomposite thesized with the mass ratio (ANI/GO) 1000:1 possessed was performed in EDOT aqueous solution containing only excellent capacitive behavior with a high specific capaci- CNTs as the dopant. The solution was stirred and ultrasoni- tance due to the unique morphology of Mace-like PANI/GO cated for 10 min before polymerization at 1.2 V for 30 s. Due composite . It seems that the low percentage of carbon to the excellent stability of the PEDOT/CNT nanocomposite nanomaterials gives better results in them of conductivity and its catalytic property towards dopamine (DA), a highly and mechanical properties. stable and sensitive DA sensor was developed that performs favorably in the presence of a high concentration of the com- Nanocomposites based on carbon nanotubes mon interferant ascorbic acid . Polypyrrole is also an interesting conducting polymer Since its discovery by Iijima in 1991, carbon nanotubes have who has the structural uniformity and high conductivity revolutionized the field of polymer nanocomposites . by strong π–π stacking between PPy conjugate backbone It was categorized as single-walled and multi-walled nano- and graphitic sidewall of CNTs. To avoid all complicated tubes. SWNTs are seamless cylinder graphite sheets. They multiple-step procedures to synthesize PPy/CNT-based have a diameter of 2 nm and a length of several microme- nanocomposites, poly(sodium 4-styrenesulfonate) (PSS) tres, while MWNTs consist of multiple layers of graphene polyelectrolyte has been added as supporting electrolytes as rolled in on themselves and separated from one another by well as dopants to improve the solubility and dispersion of 0.34 nm. Their diameter varied between 2 and 20 nm. A CNT. A one-step electrochemically polymerized method was growing number of researchers worldwide have shown an used to fabricate the PPy/PSS-CNT composite electrodes. interest in the combination of CNT with PANI. Recently, Thus, the aqueous solution for electrochemical polymeriza- review articles have been published on the progress in the tion consisted of pyrrole monomer, PSS, and long or short different synthesis methods of CNT/PANI nanocompos- CNT. Comparing to the short CNT-incorporated PPy/PSS ites. The identifications methods, the properties of the final electrodes, long CNT-incorporated PPy/PSS electrodes product, and the progress towards technological applications show the relatively more superior capacitive behavior and have been investigated [72, 73]. CNT/PANI composites can cycle stability . In other work, sodium dodecylbenzene be synthesized by electrochemical or chemical processing. sulfonate (SDBS) was used to disperse MWCNTs with ratio CNT functionality is the key to improve dispersion of the of 1:10 nanotubes to SDBS. MWCNTs, with different weight nanotubes in the liquid (aniline, solvent) and consequently in ratio (0.3, 0.5, 0.7, 0.9, and 1.1%) to the pyrrole monomer, the CNT/PANI composite. It also helps to direct formation were dispersed and sonicated in an SDBS solution. Then, of PANI chains at the surface of CNT instead of bulk PANI. PPy-MWCNTs’ layer was synthesized by electrochemical Due to their easy synthesis, processability and possibility to polymerization of distillated pyrrole on MWCNT. PPy/ combine the properties of CNT and the properties of PANI MWCNT nanocomposite was used to improve the sensi- with synergic effects, CNT/PANI composites present great tivity and selectivity of sensors via interfacial interactions interest for various applications as chemical sensors, capaci- between MWCNTs and the conducting polymer. The nano- tors, fuel cells, and electronic devices. Recently, MWCNT- composite layers were used to modify the gold layer to detect conducting polymer nanocomposites for gas-sensing appli- trace amounts of mercury (Hg), lead (Pb), and iron (Fe) ions cations were investigated. Mangu et al. demonstrated that using the surface plasmon resonance technique . Nano- the use of conducting polymers like polyaniline (PANI) and composite of PPy and carboxylated MWCNT was synthe- poly(3,4-ethylenedioxythiophene)–polystyrene sulfonic acid sized by chemical polymerization for different MWCNT (PEDOT:PSS) enhances the gas-sensing capabilities. The weight ratios. Six PPy-MWCNT nanocomposite samples 1 3 International Nano Letters (2018) 8:79–99 85 were prepared for different amounts of f-MWCNTs, and the called graphene or reduced graphene oxide. This reduc- weight ratio of functionalized MWCNT in PPy matrix varied tion can be done thermally, electrochemically, or chemi- from 0.25 to 8%. The PPy-MWCNT nanocomposite pellet cally using strong reducing agents such as hydrazine or sensors showed good sensitivity to NH gas at room tem- sodium borohydride. GO is also an attractive platform for perature. The most sensitive PPy-MWCNT nanocomposite the production of functionalized graphene platelets with sensor to NH gas was obtained with 4 wt% MWCNT ratio improved mechanical, thermal, and/or electronic proper- . Polyphenazines and poly(triphenylmethanes) as con- ties [81–84]. Ambrosi and Pumera confirmed later that the ducting polymers were also combined with CNT to develop electrochemical reduction is more interesting, because this electrochemical sensors and biosensors. Barsan et al. pub- process allows to control accurately the obtained chemi- lished recently a review on preparation and characteriza- cal structures of graphene with reproducible density of tion of conducting polymer/CNT composites based on these the oxygen functionalities PEDOT/GO nanocomposite phenazine polymers. The specific combination of phenazine/ of reduced GO-doped conducting polymer PEDOT was triphenylmethane polymers with CNT leads to an improved prepared to improve electrochemical catalytic property of performance of the resulting sensing devices because of their the resulting nanocomposite . The same nanocompos- complementary electrical, electrochemical and mechanical ite was electrodeposited on GCE and followed by elec- properties, and also due to synergistic effects. The main ana- trochemical reduction. The obtained modified electrode lytical applications as sensor were reported . was used as a sensitive sensor for DA detection without ascorbic and uric acids interference . Seekaew et al. Nanocomposites based on graphene performed a gas sensor based on graphene–PEDOT:PSS composite film. Incorporating graphene in the polymer Graphene oxide (GO) can be prepared in large scales from increased the specific adsorption surface area which has natural graphite. It was synthesized by a modified Hum- improved the NH response . The preparation and the mers method as described in the previous studies . It thermoelectric proprieties of PEDOT composites contain- is a single sheet of graphite oxide-bearing oxygen func- ing PEDOT, reduced graphene oxide (RGO), and single- tional groups on their basal planes. In recent years, GO has walled CNT (SWCNT) were also reported by Li et al. . attracted great interest because of its superior mechanical, Nanocomposites based on PPy and GO exhibited enhance- structural, and thermal properties and also its low cost ment in electrical conductivity. Bora et al. synthesized compared to other conventional carbon nanomaterials polypyrrole (PPy)/graphene oxide (GO) nanocomposites like CNT. GO can be easily dispersed in aqueous solution via liquid/liquid interfacial polymerization. The developed and act as an excellent dopant for the chemical and elec- PPy/GO nanocomposite, comparing to pure polypyrrole, trochemical polymerization of conducting polymers due has shown improvement in electrical conductivity . In to the abundance of carboxyl groups that are negatively another work, GO/PPy nanocomposites were performed charged in aqueous solution. Kim et al. demonstrated that by a one-step co-electrodeposition method. During the GO can play a role as a chemical oxidant for various CPs pyrrole electropolymerization, a negative charge of GO (polythiophene, polyaniline, and polypyrrole). In addition, was incorporated into the polymer to balance the posi- diverse graphene/CP composites (graphene/polythiophene, tive charge on the polymer. Moreover, the π–π interactions graphene/polyaniline, and graphene/polypyrrole) can between GO and PPy play a considerably role in the for- simply and rapidly be synthesized using the GO as both mation of GO/PPy nanocomposites . Overoxidized graphene precursor and chemical oxidant . Poly[3,4- polypyrrole (PPyox) was used to synthesize PPyox/gra- ethylenedioxythiophene] was largely studied to synthesize phene nanocomposite due to their cation exchange and (GO/PEDOT) nanocomposites. Luo et al. have success- molecular sieve properties. The nanocomposite-modified fully synthesized GO/PEDOT nanocomposites by cyclic GCE has been prepared and applied as dopamine sensors voltammetry using graphene oxide as dopant. The result- without the interference of ascorbic acid . GO/PPy was ing nanocomposite is highly biocompatible with neuronal also used to prepare molecularly imprinted polymer (MIP) cells . Due to their many negatively charged carboxyl for quercetin detection . In the same way, the reduced groups, GO is an excellent dopant for the electropolym- form of graphene was combined with PPy for application erization of conducting polymers. The formed film con- as supercapacitors or sensors . As example of sensor, tains functional groups promoting any modification of the Rong et al. have prepared GO/PPy by reducing GO to RGO surface of the nanocomposite film. These groups reach and polymerization of PPy using potentiostatic mode. The carboxyl groups of GO partially exposed to the surface resulted nanocomposites were applied for ammonia and 2+ of the film PEDOT/GO. Normally, GO is an electrically Pb detection . In a comparative study, properties of insulating material, but its conductivity is recovered by PANI/G and PANI/MCWNT nanocomposites were inves- restoring its network through its reduction to form what is tigated. It was proved that the charge transfer between the 1 3 86 International Nano Letters (2018) 8:79–99 PANI and carbon materials (MWCNTs and G) improved such nanocomposites have been reported in the literature as the electrical conductivity of PANI. The obtained compos- promising prototype materials for chemical sensors applica- ites have different morphologies and conductivities. It was tions, as it is summarized in Table 1. elucidated that PANI/G composite has a plate form, while PANI/MCWNT composite is tubular . An electro- chemical biosensor based on PANI/RGO nanocomposite Nanocomposites synthesized has been reported. The nanocomposite was synthesized by by combination of metal nanoparticles chemical oxidative polymerization method and was then and conducting polymers used as the sensitive layer of a DNA adsorbent for detect- 2+ ing Hg . The detection limit was 0.035 nM . Nguyen Nanocomposites based on conducting polymers (CPs) and et al. synthesized PANI grafted RGO composites via a metal nanoparticles (MNPs) are a new class of nanomateri- two-step method. First, RGO was modified with 1,3-diami- als that have received a considerable attention during the last nopropane providing reactive NH groups on surface witch decade . These nanocomposites are formed by combin- can polymerize with aniline. The formed GO–NH was ing the unique properties of MNPs and CPs, in the aim to then grafted with polymer chains by in situ chemical poly- enhance the chemical and/or physical properties. The combi- merisation. The RGO-g-PANI composites were used for nation of these materials can give rise to a new nanostructure the chemical detection of hydrogen peroxide in aqueous with novel properties and promising potential applications in solutions . The G/PANI-modified electrode allowed various fields of nanoscience and nanotechnology. Recently, selective determination of the target metals in the presence many efforts have been made to synthesize new nanocom- of bismuth Bi(III). Graphene–polyaniline (G/PANI) nano- posites of conducting polymers and metal nanoparticles with composite was used to develop an electrochemical sensor new properties and applications [105, 106]. for simultaneous detection of Zn(II), Cd(II), and Pb(II). In this part, we will give an overview about the most To prevent nanoparticle aggregation during nanocompos- method used to synthesis different metal nanoparticles such ites synthesis, they added polyvinylpyrrolidone (PVP) by as Au, Pt, Pd, Ag, Cu, and Bi. We will also discuss the main a method called reverse dropping which creates a solution parameters affecting their structural, physical, and chemi - of well-dispersed particles . Under optimal conditions, cal properties. On the other hand, a special attention will be −1 the detection limits were 1.0 µg L for Zn(II) and 0.1 µg paid to the recent advances in the synthesis of nanocompos- −1 L for both Cd(II) and Pb(II). Recently, electrospun gra- ites based on metal nanoparticles and conducting polymers phene/polyaniline/polystyrene (G/PANI/PS) nanoporous such as polythiophene (PTh), polypyrrole (PPy), polyaniline fiber-modified screen-printed carbon electrode was inves- (PANI), poly(3,4-ethylenedioxythiophene) (PEDOT), and tigated and optimized also to simultaneous determination their derivatives. We will also focus on their current catalytic 2+ 2+ of Pb and Cd in the presence of bismuth. The limits and sensing applications. −1 2+ of detection were found to be 3.30 µg L for P b and −1 2+ 4.43 µg L for Cd . Poly(diaminonaphthalene) com- Different strategies for the synthesis of metal bined with RGO was synthesized in one step using cyclic nanoparticles voltammetry. The chelating capacity of poly(1,5 diami- nonaphthalene) and the properties of RGO were used to Metal nanoparticles could be prepared using two different elaborate a lead sensor . approaches, which are bottom–up and top–down. In the first approach, the metal nanoparticles are fabricated by starting from metals atoms dissolved in aqueous or organics solu- Nanocomposites based on carbon black tion and then deposed under appropriate experimental con- ditions. In the second approach, the metal nanoparticles are Only one paper is devoted to carbon black. Mallya et al. used prepared by subdivision of bulk metals usually using physi- a nanocomposite of a novel thiophene-based conducting pol- cal methods [107, 108]. Considering the above approaches, ymer and carbon black as a volatile organic compound sen- the methods of synthesis of metal nanoparticles could be sor. The obtained sensors were tested for the determination classified to six mean methods, as shown in Fig. 5. of toluene, acetone, carbon tetrachloride, and cyclohexane The chemical reduction is considered the common and showed maximum response to toluene . Since the method reported in the literature for the synthesis of metal low cost of carbon black more research must be conducted nanoparticles, which are formed by reducing metal salts in in this area. the presence of an appropriate reducing agent and a stabi- In conclusion, the carbon nanomaterials and conduct- lizer usually a special ligand, polymer, or surfactant. The ing polymer nanocomposites are very promising materials electrochemical methods are widely used in the synthesis because of multifunctional and unique properties. Therefore, of metal nanoparticles. The metal species is dissolved in 1 3 International Nano Letters (2018) 8:79–99 87 Table 1 Typical applications of CNMs/conducting polymer nanocomposites as sensor Nanocomposite Polymer CNM Application LOD Characterization Refs. PEDOT/GO PEDOT GO Dopamine detection 39 nM EIS–SEM  MWCNT–PEDOT:PSS PEDOT:PSS MWCNT Ammonia gas sensor FTIR–SEM–TEM  MWCNT–PANI PANI SEBS/MWCNT SEBS MWCNT Temperature sensors TGA, SEM  PPyox/graphene PPyox graphene Detection of Dopamine 0.1 μM SEM  −1 MIP/GO PPy Graphene oxide Quercetin determination48 nmol L  MWNTsg-PtBMA-b-PS PS-b-PtBMA MWNTs–COOH CHCl vapor sensor FTIR, 1H NMR, TGA  XRD, TEM, SEM PEDOT/CNT PEDOT CNT Dopamine detection 20 nM SEM, CV  −1 G/PANI PANI graphene Zn(II)1 µg L SEM, FTIR, CV  −1 Cd(II)0.1 µg L −1 Pb(II)0.1 µg L −1 2+ G/PANI/PS PANI/PS graphene Simultaneous determina-3.30 µg L (Pb ) SEM, TEM, BET  2+ 2+ −1 tion of Pb and Cd4.43 µg L 2+ (Cd ) 2+ 3D-rGO@PANI PANI 3D-RGO Detection of Hg 0.035 nM XPS, SEM  Poly(DTCPA-co- poly carbon black Volatile organic com- 15 ± 10 ppm UV–vis, optical pro-  BHTBT)–CB (DTCPA- pounds (VOCs) sensor filometer contact angle co- measurements AFM, BHTBT) FEG SEM −1 GO-PANI PANI GO Carbaryl, carbofuran, 0.136 mg L CV, UV–Vis and FTIR  −1 methomyl0.145 mg L spectrometry −1 0.203 mg L PEDOT/GO PEDOT GO Mercury (II) 2.78 nM SEM, TEM  G/p-AHNSA p-AHNSA Graphene Dopamine (DA) and 2 and 3 nM CV, SWV, EIS, SEM  5-hydroxytryptamine (5-HT) aqueous or organics solution, then followed by the reduction of metal ions on an appropriate support using cyclic voltam- metric or a constant reduction potential. • Metal nanoparticles immobilized in polymer matrix In general, there are three ways to obtaining metal nan- oparticles within polymer matrix, including dispersion, deposition, and immersion. The dispersion method starts with mixing metal precursor with protective polymer and the metal ions are subsequently reduced in the solution. In deposition process, metal precursor which was mixed with protective polymer is deposited onto a substrate. • Sol–gel Sol–gel methods are also considered as a very prom- ising method for the synthesis of metals nanoparticles . During their synthesis, the experimental condi- tions including pH, nature of solvent, and temperature strongly affects on properties of the synthesized metal nanoparticles. Electromagnetic irradiation The metal nanoparticles could also be prepared using electromagnetic irradiation methods including UV, microwave, ultrasonic, and laser irradiation [110, 111]. Fig. 5 Different methods used for the synthesis of metal nanoparticles Thermal decomposition 1 3 88 International Nano Letters (2018) 8:79–99 Another way for the synthesis of metal nanoparticles solution containing monomer and metal ions. Conducting is heating volatile metal compounds in organic media or polymer–metal composites are obtained by oxidizing the gas phase. The compounds degrade and liberate metal or conjugated monomer by transition metal cations, which the corresponding metal oxide in dispersed phase. induces the simultaneous formation of both the poly- mer matrix and the metal nanoparticles. Figure 6 sum- Nanocomposites based on conducting polymers maries the most procedure used for preparation of these and metal nanoparticles nanocomposite. In addition, the electrochemical or chemical methods There are four basic strategies for the preparation of the for synthesizing conducting polymer–metal nanocompos- nanocomposites of conducting polymers and metal nano- ite are considered as well as the main factors affecting the particles as mentioned in the review of Kondeatiev et al., structure and electrochemical properties of these compos- the commonly used procedures for preparation of nanocom- ites . The size of the synthesized nanocomposite was posite are: approximately ranging from 1 to 100 nm. The shape and size Electrochemical method: the deposition of metal nano- of the nanocomposite obviously depend on methods of depo- particles into the pre-synthesized polymer film, or during sition of metal nanoparticles and the shape of conducting the electropolymerization process. polymers [40, 112]. The modification of some conducting Chemical method: the nanocomposite can also be polymers such as polythiophene (PTh), polypyrrole (PPy), performed from colloid dispersions of polymers and and polyaniline (PANI) by serval metal nanoparticles was metal nanoparticles, or in one-step synthesis from mixed reported . The obtained nanocomposites were used in Fig. 6 Schematic illustration of the most procedure for the preparation of nanocomposites based on conducting polymer and metal nanoparticle CPs/MNPs 1 3 International Nano Letters (2018) 8:79–99 89 electrochemical sensors , energy technology, batteries, 6 days) . In other work, the co-polymerization of poly- and fuel cells [115, 116]. vinylpyrrolidone and polyaniline was performed by cyclic voltammetry. The nanocomposite of gold nanoparticles with Gold nanoparticles—polymer co-polymer was synthesized by electrodeposition methods on a glassy carbon electrode (GCE) in a homogeneous three- Gold nanoparticles are widely used due to their very inter- component solution consisting of aniline, PVP, and AuNPs. esting properties and their catalytic power. The conduct- The modie fi d electrode was used as glucose biosensor [ 124]. ing polymers with gold nanoparticles as a nanostructured Recently, a nanocomposite of the self-assembly gold of materials exhibit unique electrical, optical, and catalytic nanoparticles with polystyrene-b-poly(4vinylpyridine) co- properties. These nanocomposites have been utilized for polymer has been synthesized with a size of 27 nm for (bio) heavy metal, nitrite, ammonia gas, H O , dopamine, glu- sensing applications . Spherical gold nanoparticles, 2 2 cose, ascorbic acid, and uric acid detection. Different meth- with a size of 3.5 nm, were used for preparation of glucose ods for preparation of nanocomposites AuNPs/CPs are used biosensors in the presence of conducting polymer and were such as chemical, electrochemical, thermal evaporation, successfully applied to beverages for the detection of glucose hydrothermal, and spin-coating method. At present, it has content in a linear range between 0.025 and 1.25 mM. The been found that the best way to synthesis polymer–metal detection limit was 0.025 mM . An approach to elabo- nanocomposite is the deposition of metal nanoparticles into rate a novel nanocomposite in which gold nanoparticles in the polymer film. Metal nanocomposite is formed on the small size (4.2 nm) are dispersed on polypyrrole matrix has surface or in the bulk by drop casting or incorporation of been developed by Zhang et al. . The nanocomposite pre-synthesized NPs during the electrochemical deposition has showed great potential for detecting ammonia gas at of conducting polymer, as shown in Fig. 6. HAuCl was used room temperature. In addition, the bioimprinted ds-DNA as a precursor for the preparation of AuNPs/polymer with and Au nanoparticles in the o-phenylenediamine were used a concentration from 3 to 10 mM. The size of the AuNPs to modified pencil graphite electrode as sensor for the deter - is related to Au precursor concentration, polymer/AuNPs mination of dopamine. This nanocomposite was prepared molar ratio, synthesis method, and synthesis time [117–122]. by electrochemical entrapment of ds-DNA and Au nano- Huang et al. have developed a facile and well-controlled particles in the o-phenylenediamine. The nanocomposite techniques to prepare water dispersible uniform AuNPs on was applied for the determination of dopamine in biological PANI. Uniform gold nanoparticles with a size around of samples over the range of 20–7000 nM with a detection limit 2 nm were selectively reduced on polyaniline nanofibers, of 6 nM . El-said et al. have synthesized poly(4-ami- from aqueous solution of HAuCl . The strong interaction nothiophenol) nanostructures layered on gold nanodots pat- between protonated amine and AuCl leads to an excellent terned indium tin oxide (ITO) electrode. The modified gold electrocatalytical effect. The modified electrode exhibited nanodots ITO electrode were fabricated by thermal evapora- a fast response time and high sensitivity for H O sensing tion of pure gold metal onto ITO surface through polystyrene 2 2 with a detection limit of 0.1 µM . The same authors monolayer. Then, a monolayer of 4-aminothiophenol was developed an electrochemical sensor for the oxidation of self-assembly immobilized onto the gold nanodots array/ dopamine on molybdenum disulfide nanosheets–polyani- ITO electrode by electrochemical polymerization process. line (MoS–polyaniline) composites and gold nanoparticles The size of AuNPs was 80 nm. The obtained electrode was (AuNPs)-modified glassy carbon electrode with a size of used for detection of adenine and guanine in human serum 13 nm. The graphene-like MoS–polyaniline composites were sample . The nanocomposite-based gold nanoparticles synthesized by hydrothermal method and a simple in situ are usually decorated on molecularly imprinted polymer polymerization procedure. The electrochemical sensor was membranes (MIPM). In the work of Zhang et al., MIPM applied to the dopamine detection in human urine sample was used as biomimetic molecular recognition element . Two approaches to incorporate the AuNPs with and involved in o-aminothiophenol functionalized Au nano- without pre-functionalization into covalently assembled pol- particles (ATP-AuNPs) with a size of AuNPs 4.2 nm. The ythiophene films have been reported (NPs size 14.5 ± 4 nm). modified gold electrode was used for detection of herbicide The adopted approaches involve alternate deposition of simazine (SMZ) in several real samples. The linear depend- monomeric and polymeric species for creating multilayers. ency of peak current on SMZ concentrations was observed This method has been used to develop facile method for from 0.03 to 140 μM and detection limit was estimated to nanoparticles incorporation and to facilitate direct inter- be 0.013 μM . In a recent paper, an approach for syn- action between conducting polymers and nanoparticles. thesis of PEDOT/AuNPs composite was developed by Lin Both the approaches have merits and demerits on their own et al., consisting of electropolymerization of PEDOT from depending on the film requirements. However, the prepara- solution containing gold nanoparticles and EDOT monomer tion of this nanocomposite takes a very long time (more than mixed in water solution. It was demonstrated that sensor is 1 3 90 International Nano Letters (2018) 8:79–99 highly stable, sensitive, and selective and it was used for when compared to pristine polyaniline and individual metal the detection of nitrite in tap water . Sadanandhan and colloids. The Pt–Pd nanoparticles have spherical morphol- Devaki have modified the glassy carbon electrode with PANI ogy and the particles’ size was found around of 1–7 nm. through electrochemical polymerization by cyclic voltam- The antibacterial properties depend strongly on the size of metry. Then, the gold nanoparticle AuNPs were deposited metal nanoparticles . In addition, Zhai et al. fabricated by chronoamperometry on the polymer. The performance of an electrochemical biosensor for glucose with Pt nanopar- the sensor was then tested in blood samples for simultane- ticle/polyaniline hydrogel hetero structures. This biosensor ous sensing of dopamine, ascorbic acid, serotonin, and uric was applied for glucose enzyme sensor with a wide linear acid . calibration ranging from 0.01 to 8 mM and the detection limitation of 0.7 μM . Platinum nanoparticles—polymer Silver nanoparticles—polymer The interesting properties of platinum at nanoscale dimen- sion have gained research attention due to their potential Hybrid nanocomposites based on conducting polymers (CPs) application. The platinum nanoparticles are considered and silver nanoparticles (AgNPs) have recently become a very effective as a matrix in detection of various kinds of tool in the preparation of new materials. The obtained nano- biomolecules and macromolecules such as DNA, enzymes, materials exhibit a good level of electrical conductivity as other proteins, and antibodies. The same strategies used well as tunable physical, chemical, and responsive proper- in the deposition of gold nanoparticles were used for the ties. Several conducting polymers were used to produce deposition of platinum leading to a nanoparticles with diam- these nanocomposites among them, polypyrrole (PPy), and eter ranging from 1 nm to some hundreds nm using PtCl polyaniline (PANI) . and H PtCl as a precursor. The size and the distribution In a detailed review, the strategies of fabrication of 2 6 of platinum nanoparticles on the polyaniline and polypyr- nanocomposite by combination of silver nanoparticles role have been studied by varying the polymer matrix from (AgNPs) and conducting polymers and their application nanofibers to nanotubes. The nanocomposites formed are have been reported. Various strategies for the synthesis of very sensitive to the matrix morphologies. Small polymer AgNPs were detailed such as, polyol process, solvothermal nanostructure (nanofibers) provides a large number of het- method, ultraviolet irradiation, photo-reduction technique, erogeneous nucleation sites for nucleating Pt nanoparticles, electrodeposition process, DNA template method, porous leading to better distribution and dispersion of the Pt nano- material template method, and wet chemical method. The particles (2 nM) . Mishra et al. designed a new biosen- role of various additives (inorganic anions, metal cations, sor for the detection of human C-reactive protein (αCRP), and organic molecular species) on the aspect ratio of silver by combining two types of advanced materials with com- nanowires (AgNWs) has been reported. Moreover, different plementary properties, polypyrrole film (PPy) and platinum methods for the preparation of AgNWs/conducting polymers nanoparticles (PtNPs). The long chain of PPy in the polymer composite film are reviewed like spin coating, dip coatings composite acts as a space between the biomolecules and the and electro-hydrodynamic (EHDA), simple solution mixing transducer, wherein the Pt nanoparticles help in preserving techniques, and electrospinning . Nia et al. reported a the native protein conformation and reducing the steric hin- new nanocomposite sensors based on polypyrrole (PPy) dec- drance for better probe orientation and accessibility of the orated with silver nanoparticles (AgNPs) and its application biomolecules to the analyte. The obtained nanocomposite as a non-enzymatic sensor for hydrogen peroxide (H O ) 2 2 has demonstrated a large surface area and a high perfor- detection. AgNPs–PPy was deposited on glassy carbon elec- mance towards AgαCRP detection . In the paper of trode by electrochemical method using cyclic voltammetry. Adeloju et al., the surface of the platinum electrode was The modified electrode revealed that PPy and AgNPs were first modified by thin film of platinum nanoparticles with uniformly formed and PPy was decorated with small particle a diameter of 30–40 nm priory the deposition polypyr- size of AgNPs around of 25 nm . In another appli- role film, providing large surface area for the deposition of cation, Ghanbari has modified the glassy carbon electrode ultrafine film polypyrrole. This strategy was employed to (GCE) with a pre-synthesized polypyrrole (PPy) nanofiber elaborate a biosensor for potentiometric detection of sulfite and then with AgNPs to form a nanocomposite of AgNPs/ in wine and beer samples in the linear concentration range PPy/GCE. The modified electrode was used to determina - that extends from 0.75 to 65.50 μM of sulfite, with a detec- tion of hydrazine with a detection limit of 2 µM . It tion limit of 12.4 nM, and a response time of 3–5 s . was reported in many studies that plants have potential to Boomi and co-works reported the first chemical synthesis of reduce metal ions both on their surface and in various organs the polyaniline-modified Pt–Pd nanoparticles. The obtained and tissues. Alam et al. have used Ziziphus mauritiana fruit nanocomposites exhibited improved antibacterial activity extract to synthesized sliver nanoparticle AgNPs. Then, 1 3 International Nano Letters (2018) 8:79–99 91 the enzyme of alcohol dehydrogenase (YADH) has been nanoparticles. The synthesized polypyrrole nanotubes were immobilized on chemical synthesized polyaniline-coated decorated with palladium, platinum, rhodium, or ruthenium AgNPs . This approach has been actively studied in nanoparticles by carbonization method. The catalytic activ- recent years as an alternative, efficient, inexpensive, and ity of obtained composites was proved in the reduction of environmentally safe method for producing nanoparticles 4-nitrophenol to 4-aminophenol . In addition, Hos- with specific properties. seini et al. synthesized palladium nanoparticles/poly(3,4- Zang et al. have reported the preparation of a new nano- ethylenedioxythiophene) nanofibers as a sensors for glucose composite based on AgNPs–PPy-modified attapulgite and hydrogen peroxide detection by chronoamperometric (ATP) as a clay support by in situ UV-induced dispersion method. This sensor shows a low detection limit of 1.6 µM polymerization. AgNPs with a size around of 40 nm were for glucose and 0.05 µM for H O in the range of 0.04–9 mM 2 2 obtained and the potential applications of obtained com- and 0.2–25 µM, respectively . posite nanoparticles as an antibacterial agent was explored . Recently, Bhadra et al. used polyaniline (PANI) and Other metal—polymer nanocomposites polyvinyl alcohol (PVA) with silver nanoparticles to syn- thesis the nanocomposite blend (PNPAg). Nanocomposites Besides gold, platinum, palladium, etc, others metallic nano- with lower Ag concentrations have highly aligned PNPAg particles have been studied during the last decade such as nanofibers of diameter 50–80 nm and agglomerations com- copper, bismuth, and nickel. Copper nanoparticles (CuNPs) pared to the higher concentrations of Ag and have good opti- have fascinating properties such as the good thermal and cal and electrical properties. Indeed, the room temperature electrical conductivity, nonlinear optical properties, and cost electrical conductivity of the nanocomposites increased with much less than the other metals. CuNPs are very well known Ag nanoparticles . for their potential application in cooling fluids for electronic systems, conductive inks, switches, or photochromic glasses Palladium nanoparticles—polymer in optical devices and nonlinear optical materials . In addition, the CuNPs are widely used in electrochemistry as Palladium nanoparticles (PdNPs) have been used in a variety electrode materials. The effect of copper concentration and of fields, especially as catalysts in organic reactions due to surfactants on the conductivity and stability of composite their superior chemical stability and catalytic activity . polymer-supported copper nanoparticles (CuNPs) were stud- Few works have been reported in the literature for develop- ied by Pham et al., and the nanoparticles with average diam- ing the nanocomposites by the combination of palladium eter of 56 nm were synthesized by chemical reduction in the nanoparticles (PdNPs) and conducting polymers (CPs). Pro- presence of cetyltrimethylammonium bromide (CTAB) and dromidis et al. reported a simple electroless approach for polyvinylpyrrolidone (PVP) as stabilizer. They have shown the synthesis of PdNPs incorporated in polyaniline (PANI) that these compounds prevent and protect the copper nano- via formation of a preorganized palladium polymer complex particles from the agglomeration and oxidation. The CuNPs material followed by slow reduction. The PdNPs were uni- were incorporated in PEDOT:PSS in aqueous solution to formly dispersed in the polymer with a diameter size around form conducting composite , who could be used for 5–10 nm and a large electrochemically active surface area. different applications. In situ chemical oxidation polymeri- The obtained nanocomposite was applied for electrooxida- zation method was used to synthesis copper nanoparticles tion of methanol and ethanol. The results suggest that this intercalated polyaniline nanocomposite. This nanocomposite nanocomposite could be considered as an efficient anode was used to elaborate a sensor, which was applied for gas in fuel cells . In an excellent research work, Li et al. sensing towards different gases namely NH , CO, C O , NO, 3 2 reported a facile strategy to produce a novel nanoparticulate and CH at room temperature. The sensor films exhibited a polyacetylene-supported Pd(II) catalyst [NP–Pd(II)] for use highly selective response for NH with negligible response in the aqueous Suzuki–Miyaura cross-coupling reaction, towards the other gases. Although the sensor have a draw- 2− by simply treating an aqueous solution of PdCl with back related to its sensitivity at high concentration, the satu- acetylene under ambient conditions. The nanocomposites ration of the sensor was observed at concentration exceeding reveal homogeneous distribution of the Pd(II) along the 50 ppm. The large surface area and charge transfer resulting polyacetylene and the aggregation of the NP–Pd(II) with of CuNPs intercalation in PANI matrix were the character- diameters of 2–3 nm that make this nanocomposite an ideal istics allowing the enhancement of the gas response . catalyst combining the advantages of both homogeneous The same method was used to synthesize nanocomposites and heterogeneous catalysts . Sapurina et al. recently of polypyrrole (PPy) containing copper sulfide (CuS). The reported that polypyrrole nanotubes, prepared by chemical nanocomposite was characterized by the means of FTIR, reaction in the presence of methyl orange, could be used scanning electron microscope, and X-ray diffraction, dif- as a conducting substrate for the deposition of noble-metal ferential scanning calorimetry, confirming the formation 1 3 92 International Nano Letters (2018) 8:79–99 of CuS/PPy nanocomposites with porous, granular, and of PANI–Bi O suspension causing thickness of the hybrid 2 3 globular surface morphology and crystallinity. Besides, the film and increasing concentration of surfactant leads to the thermal stability and the conductivity were also studies, increase of hydrophobicity of surfactant micelles that were indicating a better thermal stability. The dielectric behavior decreased the performance of the sensor. The LOD and increases the order ness and the packing. Despite dielectric LOQ for the pramipexole detection are 1.10 and 3.35 µg/ loss arises due to the localized motion of the charge carriers. mL, respectively . Salih et al. have modified carbon The conductivity of CuS/PPy nanocomposite increases with paste electrode (CPE) with poly(1,8-diaminonaphthalene) the increase in the concentration of CuS. The nanocompos- and bismuth film for detection of lead. The bi-poly1,8-DAN/ ites have a large scientific and technological interest and CPE was prepared and characterized by cyclic voltammetry possible application like sensors . Ternary NiO/CuO/ and electrochemical impedance spectroscopy. It was dem- PANI nanocomposites were synthesized by in situ growth onstrated that higher concentration could cause the reduc- of NiO/CuO nanoparticles via electrodeposition and elec- tion of active sites on the surface of electrode. The modi- trochemical oxidation, in a PANI matrix prepared through fied electrode was applied for the analysis of lead in water electrodeposition. Due to the large surface area and good samples using square wave voltammetry in acidic medium conductivity of NiO/CuO/PANI nanocomposite, a non- . Similarly, Elbasri et al. have fabricated the modi- enzymatic sensor exhibited high electrocatalytic activity fied poly(1,8-Diaminonaphthalene) by nickel ions particles towards the oxidation of glucose. The modified electrode (NiPs) on carbon paste electrode (CPE) for electrocatalytic displayed higher sensitivity and a lower detection limit of oxidation of methanol in alkaline medium for direct metha- 2.0 μM . MnO nanoparticles have attracted large atten- nol fuel cells (DMFCs). The obtained composite was char- tion due to its abundance and relatively environmentally acterized by scanning electron microscopy (SEM), cyclic friendly nature . To improve the capacitance property voltammetry (CV), and electrochemical impedance spec- of PEDOT, Yang et al. used manganese dioxide nanopar- troscopy (EIS) . Different metallic particles were used ticles MnO –NPs, to produce a high-performance electro- to develop a sensor for the electroanalysis of ascorbic acid chemical energy storage electrode. The PEDOT/MnO –NPs (AA). Platinum electrode modified with polyterthiophene were prepared by simple thermal treatment and chemical (P3T) and doped with metallic particles (Cu, Co, Ag, Au, vapor phase polymerization (VPP) methods. Despite the and Pd) was fabricated by first the electropolymerization of low conductivity and aggregation of MnO –NPs, the con- the monomer and then the incubation of the modified elec- trol of the loading and distribution of MnO –NPs in PEDOT trode in metallic ions solution to form the composite materi- matrix offer uniform dispersion of nanoparticles into porous als. The good sensitivity was obtained with the P3T–Ag film PEDOT matrix, which enhance the performance of the com- towards the target molecule AA, due to the high electron posite electrode . The conductive PEDOT:PSS matrix conductivity and good stability of the silver nanoparticles. −10 −1 was also used by Ju et al., with tin selenide SnSe nanosheets The limit of detection was found to be 5.1710 mol L to achieve high-performance polymer-based thermoelectric using square wave voltammetry (SWV) . devices. The subsequent solvent treatment appears a promis- The incorporation of metal nanoparticles with conduct- ing strategy to create the nanocomposites . Other nano- ing polymers has led to a significant increase in the perfor - composites based on Gallium nitride nanoparticles (GaN) mance of devices in terms of sensitivity, selectivity, multi- and poly(3,4-ethylenedioxythiophene)-co-polypyr role plexed detection capability, capacitance, and portability. In (GaN/PEDOT–PPY) were synthesized using supercritical general, nanomaterials have played a key role in chemistry, ammonia method and by chemical oxidative polymerization biology, physics, engineering, and medicine. Table 2 shows method. The nanocomposite was used as an electrochemical the characteristics and the applications as sensors and fuel catalyst for the oxidation of an antihelminthic drug meben- cells based on various nanostructured conducting polymers dazole using differential pulse voltammetry . Bismuth and nanoparticles. recognized with a low toxicity and widely used in electro- analytical as environmentally friendly electrode since the Challenges and trends first publication of Wang et al., . Bismuth nanoparti- cles were employed in synthesis of different nanocomposite The preparation, electrical characterization, and applications materials for application in different area example power of composite layers formed by dispersing carbon on metal- generation as thermoelectric material [155, 156] and electro- lic nanostructures in polymer have been described. Indeed, analysis as sensor. Polyaniline–bismuth oxide (PANI–Bi O ) the attractive properties of carbon structures such as carbon 2 3 nanocomposite was used to fabricate a sensor for the detec- paste, carbon nanotube, carbon nanofibers, and graphene tion of pramipexole in pharmaceutical formulation. The pre- make them suitable materials for polymerizations of a num- pared electrode has lower charge transfer resistance leading ber of monomers. The combination of carbon materials to higher electrocatalytic activity. A highest concentration with polymers improves the properties of these materials 1 3 International Nano Letters (2018) 8:79–99 93 Table 2 Nano-structured conducting polymer/nanoparticle-based sen- components including spectral, electronic, magnetic, opti- sors, biosensors, and other applications cal properties, and specific surface area. Some interesting papers have been devoted to the strategies employed for Metal nanoparticles/conducting polymer Application Refs. the preparation of NPs/polymers/CNMs. As mentioned by Au/polyaniline Dopamine  recent papers, multi-component nanocomposites synthesized Au/polyaniline H O  2 2 with the combination of CNMs/CPs and MNPs produce new Au/polyvinylpyrrolidone–polyaniline Glucose  materials with exciting properties such as catalysis, enhance- Pt/polypyrrole C-reactive protein  ment of mass transport, high-effective surface area, and con- Pt/poly(3,4-ethylenedioxythiophene):pol Solar cells  ductivity. Moreover, various strategies for the preparation y(styrenesulfonate) of nanocomposites have been reported [166, 174–179]. In Ag/polypyrrole Hydrazine  the light of recent works, it remains a challenge to founding Ag/polypyrrole H O  2 2 new approaches to synthesize new nanocomposite materi- Pd/polyaniline Fuel cells  als based on carbon nanoparticles or metallic nanoparticles. Ni/poly(1,8-diaminonaphthalene) Fuel cells  The idea is to improve the simplicity and efficiency of the Au/poly(3,4ethylenedioxythiophene) Cysteine  new composite and extend the application of the composite Au/poly(3,4-ethylenedioxythiophene) Solar cells  materials in different fields with a low cost. Pd/poly(diphenylbutadiene) Fuel cells  Acknowledgements This work was supported by MESRSFC (Ministère de l’Enseignement Supérieur et de la Recherche Scienti- fique et de la Formation des cadres—Morocco) and CNRST (Centre for different purposes (from electrochemical detection to fuel National pour la Recherche Scientifique et Technique—Morocco) (Pro- cell). From the work detailed in this review, it is clear also ject number PPR/2015/72). that the metallic nanoparticles such as gold, platinum, and Open Access This article is distributed under the terms of the Crea- silver combined with conducting polymers have much to tive Commons Attribution 4.0 International License (http://creat iveco offer in the different fields. However, to our best knowledge, mmons.or g/licenses/b y/4.0/), which permits unrestricted use, distribu- no comparative study covering the electropolymerization of tion, and reproduction in any medium, provided you give appropriate conducting polymer and carbon nanomaterial or metallic credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. nanoparticles was reported. The fabrication of nanocompos- ites by chemical mode takes more time in all steps of prepa- ration than electrochemical mode, either for nanoparticles synthesis or for polymerization. It could be take more than References 48 h . Furthermore, it was noted that the nanoparticles were generally synthesized by chemical ways which was 1. MacDiarmid, A.G.: “Synthetic metals”: a novel role for more difficult compared to electrochemical one . In organic polymers (nobel lecture). Angew. Chem. Int. 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