Intermetallic Pd-Y nanoparticles/N-doped carbon nanotubes as multi-active catalysts for oxygen reduction reaction, ethanol oxidation reaction, and zinc-air batteries.

Intermetallic nanomaterials are unique in terms of their band gap, atomic-level arrangement, and well-defined stoichiometry, which allows them to exhibit significantly enhanced catalytic performance in electrochemical applications. However, the preparation of durable intermetallic catalysts with a lower content of platinum group metals is challenging, while the lack of control over the loss of active components limits their long-term application due to weak interaction between the support and the nanostructure. Here, we have designed the intermetallic alloyed nanoparticles (NPs) of PdY on N-doped carbon nanotubes (PdY/NCNTs) as a multifunctional catalyst for the oxygen reduction reaction (ORR), the ethanol oxidation reaction (EOR), and zinc-air batteries (ZABs). The strong adhesion through nitrogen ensures the anchoring of alloyed PdY NPs on the NCNTs, which restrains atomic migration and sintering during their conversion to intermetallic phases. This study confirms that there is negligible active site leaching owing to the strong and multiple dative bonds between the NCNTs and PdY NPs. Therefore, this catalyst exhibits remarkable catalytic activity, resulting in a mass activity of 1317 and 2902 mA mgPd-1 at jk and jf for the ORR and the EOR, respectively, and remains stable for a longer period. In addition, the PdY/NCNT-containing air cathode-fabricated ZAB achieved a higher power density (0.236 W cm-2) compared to the benchmark Pt/C.

Multiscale Understanding of Covalently Fixed Sulfur-Polyacrylonitrile Composite as Advanced Cathode for Metal-Sulfur Batteries.

Metal-sulfur batteries (MSBs) provide high specific capacity due to the reversible redox mechanism based on conversion reaction that makes this battery a more promising candidate for next-generation energy storage systems. Recently, along with elemental sulfur (S8 ), sulfurized polyacrylonitrile (SPAN), in which active sulfur moieties are covalently bounded to carbon backbone, has received significant attention as an electrode material. Importantly, SPAN can serve as a universal cathode with minimized metal-polysulfide dissolution because sulfur is immobilized through covalent bonding at the carbon backbone. Considering these unique structural features, SPAN represents a new approach beyond elemental S8 for MSBs. However, the development of SPAN electrodes is in its infancy stage compared to conventional S8 cathodes because several issues such as chemical structure, attached sulfur chain lengths, and over-capacity in the first cycle remain unresolved. In addition, physical, chemical, or specific treatments are required for tuning intrinsic properties such as sulfur loading, porosity, and conductivity, which have a pivotal role in improving battery performance. This review discusses the fundamental and technological discussions on SPAN synthesis, physicochemical properties, and electrochemical performance in MSBs. Further, the essential guidance will provide research directions on SPAN electrodes for potential and industrial applications of MSBs.

In Situ Oriented Mn Deficient ZnMn2O4@C Nanoarchitecture for Durable Rechargeable Aqueous Zinc-Ion Batteries.

Manganese (Mn)-based cathode materials have garnered huge research interest for rechargeable aqueous zinc-ion batteries (AZIBs) due to the abundance and low cost of manganese and the plentiful advantages of manganese oxides including their different structures, wide range of phases, and various stoichiometries. A novel in situ generated Mn-deficient ZnMn2O4@C (Mn-d-ZMO@C) nanoarchitecture cathode material from self-assembly of ZnO-MnO@C for rechargeable AZIBs is reported. Analytical techniques confirm the porous and crystalline structure of ZnO-MnO@C and the in situ growth of Mn deficient ZnMn2O4@C. The Zn/Mn-d-ZMO@C cell displays a promising capacity of 194 mAh g-1 at a current density of 100 mA g-1 with 84% of capacity retained after 2000 cycles (at 3000 mA g-1 rate). The improved performance of this cathode originates from in situ orientation, porosity, and carbon coating. Additionally, first-principles calculations confirm the high electronic conductivity of Mn-d-ZMO@C cathode. Importantly, a good capacity retention (86%) is obtained with a year-old cell (after 150 cycles) at 100 mA g-1 current density. This study, therefore, indicates that the in situ grown Mn-d-ZMO@C nanoarchitecture cathode is a promising material to prepare a durable AZIB.

Nitrogen-rich graphitic-carbon@graphene as a metal-free electrocatalyst for oxygen reduction reaction.

The metal-free nitrogen-doped graphitic-carbon@graphene (Ng-C@G) is prepared from a composite of polyaniline and graphene by a facile polymerization following by pyrolysis for electrochemical oxygen reduction reaction (ORR). Pyrolysis creates a sponge-like with ant-cave-architecture in the polyaniline derived nitrogenous graphitic-carbon on graphene. The nitrogenous carbon is highly graphitized and most of the nitrogen atoms are in graphitic and pyridinic forms with less oxygenated is found when pyrolyzed at 800 °C. The electrocatalytic activity of Ng-C@G-800 is even better than the benchmarked Pt/C catalyst resulting in the higher half-wave potential (8 mV) and limiting current density (0.74 mA cm-2) for ORR in alkaline medium. Higher catalytic performance is originated from the special porous structure at microscale level and the abundant graphitic- and pyridinic-N active sites at the nanoscale level on carbon-graphene matrix which are beneficial to the high O2-mass transportation to those accessible sites. Also, it possesses a higher cycle stability resulting in the negligible potential shift and slight oxidation of pyridinic-N with better tolerance to the methanol.

Carbon nanotubes-based PdM bimetallic catalysts through N4-system for efficient ethanol oxidation and hydrogen evolution reaction.

Transitional metal-nitrogen-carbon system is a promising candidate to replace the Pt-based electrocatalyst due to its superior activity, durability and cost effectiveness. In this study, we have designed a simple strategy to fabricate carbon nanotubes-supported binary-nitrogen-carbon catalyst via wet-chemical method. Palladium and transitional metals (M, i.e. manganese cobalt and copper) nanoparticles are anchored through four-nitrogen system onto carbon nanotubes (denoted as PdM-N4/CNTs). This material has been used as bifunctional electrocatalyst for electrochemical ethanol oxidation reaction and hydrogen evolution reaction for the first time. The N4-linked nanoparticles onto carbon nanotubes plays a crucial role in intrinsic catalytic activity for both reactions in 1 M KOH electrolyte. Among three PdM-N4/CNTs catalysts, the PdMn-N4/CNTs catalyst exhibits higher catalytic activity in terms of current density, mass activity and stability compared to the benchmark Pt/C. The robust electrocatalysis are inherited from the better attachment of PdMn through N4-system onto carbon nanotubes, comparatively smaller particles formation with better dispersion and higher electrical conductivity.

Development of Highly Active Bifunctional Electrocatalyst Using Co3O4 on Carbon Nanotubes for Oxygen Reduction and Oxygen Evolution.

Replacement of precious platinum catalyst with efficient and cheap bifunctional alternatives would be significantly beneficial for electrocatalytic oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) and the application of these catalysts in fuel cells is highly crucial. Despite numerous studies on electrocatalysts, the development of bifunctional electrocatalysts with comparatively better activity and low cost remains a big challenge. In this paper, we report a nanomaterial consisting of nanocactus-shaped Co3O4 grown on carbon nanotubes (Co3O4/CNTs) and employed as a bifunctional electrocatalyst for the simultaneous catalysis on ORR, and OER. The Co3O4/CNTs exhibit superior catalytic activity toward ORR and OER with the smallest potential difference (0.72 V) between the [Formula: see text] (1.55 V) for OER and E1/2 (0.83 V) for ORR. Thus, Co3O4/CNTs are promising high-performance and cost-effective bifunctional catalysts for ORR and OER because of their overall superior catalytic activity and stability compared with 20 wt% Pt/C and RuO2, respectively. The superior catalytic activity arises from the unique nanocactus-like structure of Co3O4 and the synergetic effects of Co3O4 and CNTs.

Highly Efficient Dual Active Palladium Nanonetwork Electrocatalyst for Ethanol Oxidation and Hydrogen Evolution.

Tunable palladium nanonetwork (PdNN) has been developed for catalyzing ethanol oxidation reaction (EOR) and hydrogen evolution reaction (HER) in alkaline electrolyte. 3D PdNN is regarded as a dual active electrocatalyst for both EOR and HER for energy conversion application. The PdNN has been synthesized by the simple chemical route with the assistance of zinc precursor and a surfactant (i.e., cetyltrimethylammonium bromide, CTAB). The thickness of the network can be tuned by simply adjusting the concentration of CTAB. Both EOR and HER have been performed in an alkaline electrolyte, and characterized by different voltammetric methods. The 3D PdNN has shown 2.2-fold higher electrochemical surface area than the commercially available Pt/C including other tested catalysts with minimal Pd loading. As a result, it provides a higher density of EOR and HER active sites and facilitated the electron transport. For example, it shows 2.6-fold higher mass activity with significantly lower CO2 production for EOR and the similar overpotential (110 mV @ 10 mA cm-2) for HER compared to Pt/C with better reaction kinetics for both reactions. Thus, the PdNN is proved as an efficient electrocatalyst with better electrocatalytic activity and stability than state-of-the-art Pt/C for both EOR and HER because of the crystalline, monodispersed, and support-free porous nanonetwork.

3D graphene preparation via covalent amide functionalization for efficient metal-free electrocatalysis in oxygen reduction.

3D and porous reduced graphene oxide (rGO) catalysts have been prepared with sp3-hybridized 1,4-diaminobutane (sp3-DABu, rGO-sp3-rGO) and sp2-hybridized 1,4-diaminobenzene (sp2-DABe, rGO-sp2-rGO) through a covalent amidation and have employed as a metal-free electrocatalyst for oxygen reduction reaction (ORR) in alkaline media. Both compounds have used as a junction between functionalized rGO layers to improve electrical conductivity and impart electrocatalytic activity to the ORR resulting from the interlayer charge transfer. The successful amidation and the subsequent reduction in the process of catalyst preparation have confirmed by X-ray photoelectron spectroscopy. A hierarchical porous structure is also confirmed by surface morphological analysis. Specific surface area and thermal stability have increased after successful the amidation by sp3-DABu. The investigated ORR mechanism reveals that both functionalized rGO is better ORR active than nonfunctionalized rGO due to pyridinic-like N content and rGO-sp3-rGO is better ORR active than rGO-sp2-rGO due to higher pyridinic-like N content and π-electron interaction-free interlayer charge transfer. Thus, the rGO-sp3-rGO has proven as an efficient metal-free electrocatalyst with better electrocatalytic activity, stability, and tolerance to the crossover effect than the commercially available Pt/C for ORR.

New Approach for Porous Chitosan-Graphene Matrix Preparation through Enhanced Amidation for Synergic Detection of Dopamine and Uric Acid.

Amide-functionalized materials have emerged as promising nonprecious catalysts for electrochemical sensing and catalysis. The covalent immobilization of chitosan (CS) onto graphene sheet (GS) (denoted as CS-GS) has been done via higher degree of amidation reaction to develop an electrochemical sensing matrix for simultaneous determination of dopamine (DA) and uric acid (UA). The enhanced amidation between CS and GS has not been reported previously. However, electrochemical results have revealed that the CS-GS enhances the electrocatalytic performance in terms of the oxidation potential and peak current due to the higher degree of amide functionalization compared to that of CS/GS, which has a lower amidation. Differential pulse voltammetry-based studies have indicated that the CS-GS matrix works at a lower detection limit (0.14 and 0.17 µM) (S/N = 3) and over a longer linear range (1-700 and 1-800 µM), with a comparatively higher sensitivity (2.5 and 2.0 µA µM-1 cm-2), for DA and UA, respectively. In addition, the CS-GS matrix demonstrates good selectivity toward the detection of DA and UA in the presence of a 10-fold higher concentration of AA and glucose. The as-prepared three-dimensional porous CS-GS also endows selective determination toward DA and UA in various real samples.

Electrochemical Sensing of Monohydric Alcohols on Different Linkers Imbedded in Between Graphene and Platinum Nanoparticles.

We investigated the relationship between the linker's length and the electrooxidation of methanol and ethanol with PtNPs-decorated graphene oxide (GO). The covalently functionalized materials were prepared with three different lengths of the alkane chain as the linker molecules in between GO and platinum nanoparticles (PtNPs). Electrochemically reduced GO-S-(CH2)n-S-Pt [ERGO-S-(CH2)n- S-Pt, wherein n = 2, 3 and 4] was obtained via electrochemical reduction of GO-S-(CH2)1-S-Pt in PBS at pH 5. ERGO-S-(CH2)n-S-Pt was characterized by XPS and FE-SEM. The XPS result reveals that the Pt at% increased with the increasing of chain length and the surface morphology indicates the surface area increased with the increasing of linker's length. The electrochemical behavior of these modified glassy carbon electrodes (GCEs) were investigated using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and chronoamperometry (CA). The ERGO-S-(CH2)n-S-Pt was employed to detect methanol and ethanol; and the ERGO-S-(CH2)4-S-Pt showed a better performance towards alcohol oxidation reaction (AOR) among all ERGO-S-(CH2)n- S-Pt. The detection limit of methanol and ethanol was 1.8 x 10⁻² mM and 1.28 x 10⁻² mM, respectively, at ERGO-S-(CH2)4-S-Pt.

Manganese Dioxide/Reduced Graphene Oxide with Poly(3,4-ethylenedioxythiophene) for Improved Electrocatalytic Oxygen Reduction Reaction.

Poly(3,4-ethylenedioxythiophene)-(PEDOT)-functionalized reduced graphene oxide (rGO) with MnO2 nanoparticles (MnO2/PEDOT/rGO) was prepared using electrochemical methods. The MnO2/ PEDOT/rGO was obtained through the electrochemical reduction of PEDOT/GO and under electrochemical treatment in KMnO4. The PEDOT/rGO and MnO2/PEDOT/rGO were characterized by several instrumental and electrochemical methods. The electrocatalytic 02 reduction for both electrodes was investigated via cyclic and hydrodynamic voltammetry in 0.1 M KOH aqueous solutions. The kinetic analysis in comparison to PEDOT/rGO a significant enhancement was found for the MnO2/PEDOT/rGO. The proposed main path in the oxygen reduction reaction (ORR) mechanism on the MnO2/PEDOT/rGO was the direct four-electron transfer process with faster transfer kinetic rate. The better ORR kinetics were obtained due to the excellent composite formation and well attachment of MnO2 NPs within oxide form. The PEDOT/rGO was less stable for long term use than MnO2/PEDOT/rGO.

High catalytic activity of electrochemically reduced graphene composite toward electrochemical sensing of Orange II.

Orange II, an azo dye, is sometimes illegally used as a red dye in food products despite its adverse health effects if consumed. Therefore, the determination of low concentrations of Orange II is an important target. An Orange II sensor was prepared using electrochemically reduced graphene oxide grafted with 5-amino-1,3,4-thiadiazole-2-thiol-Pt nanoparticles (denoted as ERGO-ATDT-Pt) onto a glassy carbon electrode (GCE) and investigated for Orange II detection in 0.1M acetate buffer solution (ABS at pH 4.5) with prominent reversible redox peaks. A wide linear range of 1×10(-)(8)-6×10(-)(7)M with a low detection limit of 3.4×10(-)(10)M (s/n=3) was found for Orange II detection. This developed ERGO-ATDT-Pt/GCE sensor showed good selectivity, excellent stability and better response to the real sample analysis with excellent recovery.

A green preparation of nitrogen doped graphene using urine for oxygen reduction in alkaline fuel cells.

A simple, eco-friendly and efficient harmless chemical approach has been developed for the simultaneous nitrogen (N) doping and reduction of graphene oxide (GO) by cost free human urine using simple refluxing. Large-scale preparation of graphene has been hindered largely by several issues, such as highly toxic reducing agents that are harmful to human health and environment, complicated reduction process and costly chemicals. Human urine is a natural precursor of urea with no cost. In this process, the NH3 has acted as not only reducing but also doping agent that produced via thermal decomposition of urea, while the N doping level of ~11.1 at% is achieved. For the first time we have used urine as a reductant and doping agent in such a high class chemical technology. The simultaneous reduction and N-doping of GO using urine (denoted as UNG) have confirmed by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, and UV-vis spectroscopy. The resultant UNG has demonstrated to show remarkable electrocatalytic activity toward oxygen reduction reaction (ORR) with better fuel selectivity, and stability than that of the commercially available 20 wt% Pt/C electrode using cyclic voltammetry (CV) and chronoamperometry.

The nanostructure of nitrogen atom linked carbon nanotubes with platinum employed to the electrocatalytic oxygen reduction.

Multi-walled carbon nanotube grafted Pt nanoparticles via nitrogen atom (MWCNT-N-Pt) has chemically synthesized and characterized as an efficient oxygen reduction reaction (ORR) catalysts. Structural and morphological properties of the electrocatalyst have characterized by transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS) techniques. The electrochemical properties have evaluated using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and hydrodynamic voltammetry techniques. The electrochemical properties toward ORR of MWCNT-N-Pt have evaluated in 0.1 mol L(-1) HClO4 aqueous solution. The electrocatalytic reduction of O2 at the MWCNT-N-Pt catalyst establishes a pathway of four-electron transfer reduction into H2O. Hydrodynamic voltammetry reveals that the modified electrode has catalyzed effectively at higher potential. The value of transferred electron number and other kinetic parameters have demonstrated that the MWCNT-N-Pt is highly facilitated than that of bulk Pt to electrocatalytic oxygen reduction with comparatively low Pt content (27.04 Wt%) and higher electrochemical surface area (ESA(Pt)) 94.34 m2 gPt(-1).

Covalent hybridization of thiolated graphene sheet and platinum nanoparticles for electrocatalytic oxygen reduction reaction.

A covalently bonded thiolated graphene sheet-supported platinum electrocatalyst (GOS-Pt) has synthesized for electrochemical oxygen reduction reaction (ORR) in neutral media. The catalyst's structural features are characterized by transmission electron microscopy (TEM), energy dispersive X-ray (EDX), and X-ray photoelectron spectroscopy (XPS). Its activity towards the ORR has investigated by using cyclic voltammetry (CV), rotating disk electrode (RDE), and rotating ring disk electrode (RRDE) in 0.1 mol l(-1) phosphate buffer solution (PBS) at pH 7, which is also used to assess the catalyst's kinetic parameters. On a glassy carbon electrode (GCE), the catalyst shows a significant catalytic activity, with its electrocatalysis of O2 reduction occurring via four-electron transfer reduction to H2O with minimal generation of H2O2.

Poly-cobalt[tetrakis(o-aminophenyl)porphyrin] nanowire and single-walled carbon nanotube for the analysis of hydrogen peroxide.

Nanowires of poly-cobalt[tetrakis(o-aminophenyl)porphyrin] (PCoTAPPNW) were fabricated by electrochemical polymerization by the cyclic voltammetric method in anodic aluminum oxide membranes. A glassy carbon electrode (GCE) modified by PCoTAPPNW and single-walled carbon nanotubes (SWNT) without any binder was investigated with voltammetric methods in phosphate buffer saline (PBS) at pH 7.4. The PCoTAPPNW + SWNT/GCE exhibited strongly enhanced voltammetric and amperometric sensitivity towards hydrogen peroxide (H2O2), which shortened the response time (< 5 seconds), showed detection limit of 1.0 microM and enhanced the sensitivity for H2O2 detection with 194 microA mM(-1) cm(-2). The PCoTAPPNW + SWNT/GCE can be used to monitor H2O2 at very low concentration in physiological pH as an efficient electrochemical H2O2 sensor.

Determination of serotonin on a glassy carbon electrode modified by electropolymerization of meso-tetrakis(2-aminophenyl)porphyrin and single walled carbon nanotubes.

A chemically modified electrode [poly(TAPP)-SWNT/GCE] was prepared by electropolymerization of meso-tetrakis(2-aminophenyl)porphyrin (TAPP)-single walled carbon nanotubes (SWNT) on the surface of a glassy carbon electrode (GCE). This modified electrode was employed as an electrochemical biosensor for the determination of serotonin concentration and exhibited a typical enhance effect on the current response of serotonin and lower oxidation overpotential. The biosensor was very effective to determined 5-HT in a mixture. The linear response was in the range 2.0 x 10(-7) to 1.0 x 10(-5) M, with a correlation coefficient of 0.999 [i(p)(microA) = 3.406 C (microM)+0.132] on the anodic current, with a detection limit of 1 x 10(-9) M. Due to the relatively low currents and different potentials in the electrochemical responses to ascorbic acid and dopamine, the modified electrode is a useful and effective sensing device for the selective and sensitive serotonin determination in the presence of ascorbic acid and dopamine.

Reductive determination of hydrogen peroxide with MWCNTs-Pd nanoparticles on a modified glassy carbon electrode.

This paper introduces the use of multi walled carbon nanotubes (MWCNTs) with palladium (Pd) nanoparticles in the electrocatalytic reduction of hydrogen peroxide (H(2)O(2)). We have developed and characterized a biosensor for H(2)O(2) based on Nafion(®) coated MWCNTs-Pd nanoparticles on a glassy carbon electrode (GCE). The Nafion(®)/MWCNTs-Pd/GCE electrode was easily prepared in a rapid and simple procedure, and its application improves sensitive determination of H(2)O(2). Characterization of the MWCNTs-Pd nanoparticle film was performed with transmission electron microscopy (TEM), Raman, and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry (CV) and amperometry (at an applied potential of -0.2V) measurements were used to study and optimize performance of the resulting peroxide biosensor. The proposed H(2)O(2) biosensor exhibited a wide linear range from 1.0 µM to 10 mM and a low detection limit of 0.3 µM (S/N=3), with a fast response time within 10s. Therefore, this biosensor could be a good candidate for H(2)O(2) analysis.