Synergistically enhancing electrocatalysis and non-enzymatic sensing for glucose by iridium single-atom/nickel oxide/N-doped graphene.

The development of novel catalyst with high catalytic activity is important for electrochemical non-enzymatic glucose sensing. Here, iridium single-atom/nickel oxide nanoparticle/N-doped graphene nanosheet (Ir1/NiO/NG) with the loading of 1.13 wt% Ir was successfully synthesized for constructing electrochemical non-enzymatic glucose sensor for the first time. The morphology and structure of Ir1/NiO/NG were characterized by XRD, SEM, TEM, HRTEM, and XPS, and the presence of Ir SAs was confirmed by AC-HAADF-STEM. The Ir1/NiO/NG shows 65 mV lower oxidation potential and 3.3 times higher response current than Ni(OH)2/NG. In addition, Ir1/NiO/NG exhibits high sensitivity (70.09 µA mM-1 cm-2), excellent selectivity, low detection limit (2.00 µM), and great stability (91.53% current remaining after 21 days) for electrochemical non-enzymatic glucose sensing. The outstanding catalytic and sensing performance of Ir1/NiO/NG is mainly attributed to synergistic effect of Ir SAs, NiO nanoparticles, and highly conductive NG, which modulate the electronic and geometric structure of Ir1/NiO/NG. This work shows the promising potential of SACs in electrochemical sensing.

Tailoring the d-band center on Ru1Cu single-atom alloy nanotubes for boosting electrochemical non-enzymatic glucose sensing.

The development of cost-effective and highly efficient electrocatalysts is critical to help electrochemical non-enzymatic sensors achieve high performance. Here, a new class of catalyst, Ru single atoms confined on Cu nanotubes as a single-atom alloy (Ru1Cu NTs), with a unique electronic structure and property, was developed to construct a novel electrochemical non-enzymatic glucose sensor for the first time. The Ru1Cu NTs with a diameter of about 24.0 nm showed a much lower oxidation potential (0.38 V) and 9.0-fold higher response (66.5 µA) current than Cu nanowires (Cu NWs, oxidation potential 0.47 V and current 7.4 µA) for glucose electrocatalysis. Moreover, as an electrochemical non-enzymatic glucose sensor, Ru1Cu NTs not only exhibited twofold higher sensitivity (54.9 µA mM-1 cm-2) and wider linear range (0.5-8 mM) than Cu NWs, but also showed a low detection limit (5.0 µM), excellent selectivity, and great stability. According to theoretical calculation results, the outstanding catalytic and sensing performance of Ru1Cu NTs could be ascribed to the upshift of the d-band center that helped promote glucose adsorption. This work presents a new avenue for developing highly active catalysts for electrochemical non-enzymatic sensors.

Boosting Electrochemical Catalysis and Nonenzymatic Sensing Toward Glucose by Single-Atom Pt Supported on Cu@CuO Core-Shell Nanowires.

It is critical to develop high-performance electrocatalyst for electrochemical nonenzymatic glucose sensing. In this work, a single-atom Pt supported on Cu@CuO core-shell nanowires (Pt1 /Cu@CuO NWs) for electrochemical nonenzymatic glucose sensor is designed. Pt1 /Cu@CuO NWs exhibit excellent electrocatalytic oxidation toward glucose with 70 mV lower onset potential (0.131 V) and 2.4 times higher response current than Cu NWs. Sensors fabricated using Pt1 /Cu@CuO NWs also show high sensitivity (852.163 µA mM-1 cm-2 ), low detection limit (3.6 µM), wide linear range (0.01-5.18 µM), excellent selectivity, and great long-term stability. The outstanding sensing performance of Pt1 /Cu@CuO NWs, investigated by experiments and density functional theory (DFT) calculations, is attributed to the synergistic effect between Pt single atoms and Cu@CuO core-shell nanowires that generates strong binding energy of glucose on the nanowires. The work provides a new pathway for exploring highly active SACs for electrochemical nonenzymatic glucose sensor.

Single-Atom Pt Boosting Electrochemical Nonenzymatic Glucose Sensing on Ni(OH)2/N-Doped Graphene.

Conventional nanomaterials in electrochemical nonenzymatic sensing face huge challenge due to their complex size-, surface-, and composition-dependent catalytic properties and low active site density. In this work, we designed a single-atom Pt supported on Ni(OH)2 nanoplates/nitrogen-doped graphene (Pt1/Ni(OH)2/NG) as the first example for constructing a single-atom catalyst based electrochemical nonenzymatic glucose sensor. The resulting Pt1/Ni(OH)2/NG exhibited a low anode peak potential of 0.48 V and high sensitivity of 220.75 µA mM-1 cm-2 toward glucose, which are 45 mV lower and 12 times higher than those of Ni(OH)2, respectively. The catalyst also showed excellent selectivity for several important interferences, short response time of 4.6 s, and high stability over 4 weeks. Experimental and density functional theory (DFT) calculated results reveal that the improved performance of Pt1/Ni(OH)2/NG could be attributed to stronger binding strength of glucose on single-atom Pt active centers and their surrounding Ni atoms, combined with fast electron transfer ability by the adding of the highly conductive NG. This research sheds light on the applications of SACs in the field of electrochemical nonenzymatic sensing.

Three-dimensional nitrogen-doped multiwall carbon nanotube sponges with tunable properties.

A three-dimensional (3D) nitrogen-doped multiwall carbon nanotube (N-MWCNT) sponge possessing junctions induced by both nitrogen and sulfur was synthesized by chemical vapor deposition (CVD). The formation of "elbow" junctions as well as "welded" junctions, which are attributed to the synergistic effect of the nitrogen dopant and the sulfur promoter, plays a critically important role in the formation of 3D nanotube sponges. To the best of our knowledge, this is the first report showing the synthesis of macroscale 3D N-MWCNT sponges. Most importantly, the diameter of N-MWCNT can be simply controlled by varying the concentration of sulfur, which in turn controls both the sponge's mechanical and its electrical properties. It was experimentally shown that, with increasing diameter of N-MWCNT, the elastic modulus of the sponge increased while the electrical conductivity decreased. The mechanical behaviors of the sponges have also been quantitatively analyzed by employing strain energy function modeling.

Free-Standing N-Doped Porous Carbon Fiber Membrane Derived From Zn-MOF-74: Synthesis and Application as Anode for Sodium-Ion Battery With an Excellent Performance.

It is important to develop new energy storage and conversion technology to mitigate the energy crisis for the sustainable development of human society. In this study, free-standing porous nitrogen-doped carbon fiber (PN-CF) membranes were obtained from the pyrolysis of Zn-MOF-74/polyacrylonitrile (PAN) composite fibers, which were fabricated in situ by an electrospinning technology. The resulting free-standing fibers can be cut into membrane disks and directly used as an anode electrode without the addition of any binder or additive. The PN-CFs showed great reversible capacities of 210 mAh g-1 at a current density of 0.05 A g-1 and excellent cyclic stability of 170.5 mAh g-1 at a current density of 0.2 A g-1 after 600 cycles in sodium ion batteries (SIBs). The improved electrochemical performance of PN-CFs can be attributed to the rich porous structure derived by the incorporation of Zn-MOF-74 and nitrogen doping to promote sodium ion transportation.

Stable, conductive supramolecular composite of graphene sheets with conjugated polyelectrolyte.

Supramolecularly functionalized graphene-based materials with conjugated poly(2,5-bis (3-sulfonatopropoxy)-1,4-ethynylphenylene-alt-1,4-ethynylphenylene) polyelectrolyte were successfully obtained and exhibited high conductivity and stability (even for 8 months without any aid of free polymer in solution). The excellent aqueous solubility and the possibility for self-assembly through electrostatic interactions (i.e., layer-by-layer assembly) will be realized through various applications of graphene. In addition, PPE-SO(3)(-) molecules exhibit interesting optoelectronic properties, making the resulting graphene-based materials potentially useful in a variety of optoelectronic device applications.

Direct electrochemistry of glucose oxidase and biosensing for glucose based on graphene.

We first reported that polyvinylpyrrolidone-protected graphene was dispersed well in water and had good electrochemical reduction toward O(2) and H(2)O(2). With glucose oxidase (GOD) as an enzyme model, we constructed a novel polyvinylpyrrolidone-protected graphene/polyethylenimine-functionalized ionic liquid/GOD electrochemical biosensor, which achieved the direct electron transfer of GOD, maintained its bioactivity and showed potential application for the fabrication of novel glucose biosensors with linear glucose response up to 14 mM.

Water-soluble graphene covalently functionalized by biocompatible poly-L-lysine.

Graphene sheets functionalized covalently with biocompatible poly-l-lysine (PLL) were first synthesized in an alkaline solution. PLL-functionalized graphene is water-soluble and biocompatible, which makes it a novel material promising for biological applications. Graphene sheets played an important role as connectors to assemble these active amino groups of poly-l-lysine, which provided a very biocompatible environment for further functionalization, such as attaching bioactive molecules. As an example, an amplified biosensor toward H(2)O(2) based on linking peroxidase onto PLL-functionalized graphene was investigated.

Covalent functionalization of polydisperse chemically-converted graphene sheets with amine-terminated ionic liquid.

A facile method to obtain polydisperse chemically-converted graphene sheets that are covalently functionalized with ionic liquid was reported -- the resulting graphene sheets, without any assistance from polymeric or surfactant stabilizers, can be stably dispersed in water, DMF, and DMSO.

Graphene Oxides Used as a New "Dual Role" Binder for Stabilizing Silicon Nanoparticles in Lithium-Ion Battery.

For the first time, we report that graphene oxide (GO) can be used as a new "dual-role" binder for Si nanoparticles (SiNPs)-based lithium-ion batteries (LIBs). GO not only provides a graphene-like porous 3D framework for accommodating the volume changes of SiNPs during charging/discharging cycles, but also acts as a polymer-like binder that forms strong chemical bonds with SiNPs through its Si-OH functional groups to trap and stabilize SiNPs inside the electrode. Leveraging this unique dual-role of GO binder, we fabricated GO/SiNPs electrodes with remarkably improved performances as compared to using the conventional polyvinylidene fluoride (PVDF) binder. Specifically, the GO/SiNPs electrode showed a specific capacity of 2400 mA h g-1 at the 50th cycle and 2000 mA h g-1 at the 100th cycle, whereas the SiNPs/PVDF electrode only showed 456 mAh g-1 at the 50th cycle and 100 mAh g-1 at 100th cycle. Moreover, the GO/SiNPs film maintained its structural integrity and formed a stable solid-electrolyte interphase (SEI) film after 100 cycles. These results, combined with the well-established facile synthesis of GO, indicate that GO can be an excellent binder for developing high performance Si-based LIBs.

Development of Conjugated Polymers for Memory Device Applications.

This review summarizes the most widely used mechanisms in memory devices based on conjugated polymers, such as charge transfer, space charge traps, and filament conduction. In addition, recent studies of conjugated polymers for memory device applications are also reviewed, discussed, and differentiated based on the mechanisms and structural design. Moreover, the electrical conditions of conjugated polymers can be further fine-tuned by careful design and synthesis based on the switching mechanisms. The review also emphasizes and demonstrates the structure-memory properties relationship of donor-acceptor conjugated polymers for advanced memory device applications.

Facile synthesis of a large quantity of graphene by chemical vapor deposition: an advanced catalyst carrier.

A large quantity of highly conductive graphene was prepared by a novel CVD method with nickel powder as a template and PMMA as carbon source. With Pt as a model, PtNP-modified graphene showed much better electrocatalytic ability for O(2) and methanol than PtNP-reduced graphene oxide (RGO) and commercial Pt/C, showing that this graphene is a better catalyst carrier than RGO and commercial carbon.

Functionalization of graphene with electrodeposited Prussian blue towards amperometric sensing application.

Prussian blue (PB) was grown compactly on graphene matrix by electrochemical deposition. The as-prepared PB-graphene modified glassy carbon electrode (PB-graphene/GCE) showed excellent electrocatalytic activity towards both the reduction of hydrogen peroxide and the oxidation of hydrazine, which could be attributed to the remarkable synergistic effect of graphene and PB. The PB-graphene/GCE showed sensitive response to H(2)O(2) with a wide linear range of 10-1440 µM at 0.0V, and to hydrazine with a wide linear range of 10-3000 µM at 0.35 V. The detection limit was 3 µM and 7 µM, respectively, and both of them had rapid response within 5s to reach 95% steady state response. The wide linear range, good selectivity and long-time stability of the PB-graphene/GCE make it possible for the practical amperometric detection of hydrogen peroxide and hydrazine.

Electrochemical determination of morphine at ordered mesoporous carbon modified glassy carbon electrode.

A sensitive electrochemical detection scheme for morphine has been proposed by utilizing the ordered mesoporous carbon modified glassy carbon electrode (OMC/GCE). The electrochemical behaviour of morphine at the OMC/GCE was investigated by cyclic voltammetry. The modified electrode displayed a decrease in the overpotential (ca. 82mV) and an obvious increase in the peak current (80 times) compared to the bare glassy carbon electrode (GCE). The results indicated that OMC/GCE remarkably enhanced electrocatalytic activity towards the oxidation of morphine. Linear response was found over the range from 0.1 microM to 20 microM with a high sensitivity of 1.74 microA/microM and low detection limit of 10 nM (S/N=3). And the relative standard deviation was 0.86% (n=5). Moreover, combining with a medium-exchange procedure, the OMC/GCE has also been successfully applied to the selective determination of morphine in urine samples with a low detection limit of 50 nM and satisfied recovery of 96.4%. The good results indicate that the OMC/GCE holds great promise in practical application.

Electrochemical determination of NADH and ethanol based on ionic liquid-functionalized graphene.

It is firstly reported that low-potential NADH detection and biosensing for ethanol are achieved at an ionic liquid-functionalized graphene (IL-graphene) modified electrode. A substantial decrease (440 mV) in the overvoltage of the NADH oxidation was observed using IL-graphene/chitosan coating, with oxidation starting at ca. 0 V (vs. Ag|AgCl). And the NADH amperometric response at such a modified electrode is more stable (95.4% and 90% of the initial activity remaining after 10 min and 30 min at 1 mM NADH solution) than that at bare electrode (68% and 46%). Furthermore, the IL-graphene/chitosan-modified electrode exhibited a good linearity from 0.25 to 2 mM and high sensitivity of 37.43 microA mM(-1)cm(-2). The ability of IL-graphene to promote the electron transfer between NADH and the electrode exhibited a novel and promising biocompatible platform for development of dehydrogenase-based amperometric biosensors. With alcohol dehydrogenase (ADH) as a model, the ADH/IL-graphene/chitosan-modified electrode was constructed through a simple casting method. The resulting biosensor showed rapid and highly sensitive amperometric response to ethanol with a low detection limit (5 microM). Moreover, the proposed biosensor has been used to determine ethanol in real samples and the results were in good agreement with those certified by the supplier.

Graphene/AuNPs/chitosan nanocomposites film for glucose biosensing.

A novel glucose biosensor based on immobilization of glucose oxidase in thin films of chitosan containing nanocomposites of graphene and gold nanoparticles (AuNPs) at a gold electrode was developed. The resulting graphene/AuNPs/chitosan composites film exhibited good electrocatalytical activity toward H(2)O(2) and O(2). The wide linear response to H(2)O(2) ranging from 0.2 to 4.2 mM (R=0.998) at -0.2V, high sensitivity of 99.5 microA mM(-1) cm(-2) and good reproducibility were obtained. The good electrocatalytical activity might be attributed to the synergistic effect of graphene and AuNPs. With glucose oxidase (GOD) as a model, the graphene/AuNPs/GOD/chitosan composite-modified electrode was constructed through a simple casting method. The resulting biosensor exhibited good amperometric response to glucose with linear range from 2 to 10 mM (R=0.999) at -0.2V and from 2 to 14 mM (R=0.999) at 0.5 V, good reproducibility and detection limit of 180 microM. Glucose concentration in human blood was studied preliminarily. From 2.5 to 7.5 mM, the cathodic peak currents of the biosensor decrease linearly with increasing the glucose concentrations. The graphene/AuNPs/GOD/chitosan composites film shows prominent electrochemical response to glucose, which makes a promising application for electrochemical detection of glucose.

Preparation of gold nanoparticles/functionalized multiwalled carbon nanotube nanocomposites and its glucose biosensing application.

Gold nanoparticles stabilized by amino-terminated ionic liquid (Au-IL) have been in situ noncovalently deposited on poly(sodium 4-styrene-sulfonate) (PSS)-functionalized multiwalled carbon nanotubes (MWCNTs) to form a MWCNTs/PSS/Au-IL nanocomposite. PSS can interact with MWCNTs through hydrophobic interaction. Amino-terminated ionic liquid was applied to reduce aqueous HAuCl(4), and the resulting gold nanoparticles were attached to the PSS-functionalized MWCNTs simultaneously. Most gold nanoparticles dispersed well on the functionalized MWCNTs. Transmission electron microscopy, Raman and X-ray photoelectron spectroscopy were used to confirm the composition and structure of the nanocomposites. The resulting MWCNTs/PSS/Au-IL composite exhibits good electrocatalysis toward oxygen and hydrogen peroxide reduction. And good biocompatibility with glucose oxidase was also demonstrated due to its good biocatalysis toward glucose substrate, which offered a friendly environment for the immobilization of biomolecules. Such bionanocomposite provides us potential applications in fabrication of biosensors. The resulting biosensor exhibits good response to glucose with a low detection limit 25 microM. It also has excellent reproducibility, satisfied operational stability and good storage stability.

Carbon nanotube/gold nanoparticles/polyethylenimine-functionalized ionic liquid thin film composites for glucose biosensing.

A novel glucose biosensor based on immobilization of glucose oxidase (GOD) in thin films of polyethylenimine-functionalized ionic liquid (PFIL), containing a mixture of carbon nanotubes (CNT) and gold nanoparticles (AuNPs) and deposited on glassy carbon electrodes, was developed. Direct electrochemistry of glucose oxidase in the film was observed, with linear glucose response up to 12mM. The PFIL-stabilized gold nanoparticles had a diameter of 2.4+/-0.8nm and exhibited favorable stability (stored even over one month with invisible change in UV-vis spectroscopic measurements). In addition, CNT were also well dispersed in the PFIL matrix, then, the resulting CNT/AuNPs/PFIL composites film showed high electrocatalytic activity toward reduction of hydrogen peroxide and oxygen. Here, PFIL, due to its high ionic conductivity, good solubility to CNT, and stability to nanoparticles, played an important role in constructing stable CNT/AuNPs/PFIL/GOD composites. And good biocompatibility of PFIL also offered a friendly environment for the immobilization of biomolecules.

Size-controlled synthesis of monodispersed gold nanoparticles stabilized by polyelectrolyte-functionalized ionic liquid.

The size-controlled synthesis of monodispersed gold nanoparticles (AuNPs) stabilized by polyelectrolyte-functionalized ionic liquid (PFIL) is described. The resulting AuNPs' size, with a narrow distribution, can be tuned by the concentration of HAuCl(4). Such PFIL-stabilized AuNPs (PFIL-AuNPs) showed a high stability in water at room temperature for at least one month; they were also quite stable in solutions of pH 7-13 and high concentration of NaCl. In addition, the PFIL-AuNPs exhibited obvious electrocatalytical activity toward ß-nicotinamide adenine dinucleotide (NADH for short, a cofactor in enzymatic reactions of NAD(+)/NADH(-)-dependent dehydrogenases) oxidation, suggesting a potential application for bioelectroanalysis.