High Catalytic Activity of Amorphous Ir-Pi for Oxygen Evolution Reaction

Large-scale production of hydrogen gas by water electrolysis is hindered by the sluggish kinetics of oxygen evolution reaction (OER) at the anode. The development of a highly active and stable catalyst for OER is a challenging task. Electrochemically prepared amorphous metal-based catalysts have gained wide attention after the recent discovery of a cnbalt-phosphate (Co-Pi) catalyst: Herein, an amorphous iridium-phosphate (Ir-Pi) is investigated as an oxygen evolution catalyst. The catalyst is prepared by the anodic polarization of carbon paper electrodes in neutral phosphate buffer solutions containing IrCl3. The Ir-Pi film deposited on the substrate has significant amounts of phosphate and It centers in an oxidation state higher than +4. Phosphate plays a significant role in the deposition of the catalyst and also in its activity toward OER. The onset potential of OER on the Ir-Pi is about 150 mV lower in comparison with the Co-Pi under identical experimental conditions. Thus, Ir-Pi is a promising catalyst for electrochemical oxidation of water.

Photoelectrochemical degradation of eosin yellowish dye on exfoliated graphite-ZnO nanocomposite electrode

In the quest for harnessing more power from the sun for water treatment by photoelectrochemical degradation, we prepared a novel photoanode of exfoliated graphite (EG)-ZnO nanocomposite. The nanocomposite was characterised by X-ray diffractometry, energy dispersive spectroscopy, Brunauer-Emmett-Teller surface area analyser, thermal gravimetric analyser, and X-ray photoelectron spectroscopy. The EG-ZnO nanocomposite was fabricated into a photoanode and applied for the photoelectrochemical degradation of 0.1 x 10(-4) M eosin yellowish dye in 0.1 M Na2SO4 under visible light irradiation. The degradation was monitored with a visible spectrophotometer. The photoelectrochemical degradation process resulted in enhanced degradation efficiency of ca. 93 % with kinetic rate of 11.0 x 10(-3) min(-1) over photolysis and electrochemical oxidation processes which exhibited lower degradation efficiencies of 35 and 40 % respectively.

Functionalization of Si(111) surfaces and the formation of mixed monolayers for the covalent attachment of molecular catalysts in photoelectrochemical devices

The functionalization of silicon surfaces with molecular catalysts for proton reduction is an important part of the development of a solar-powered, water-splitting device for solar fuel formation. The covalent attachment of these catalysts to silicon without damaging the underlying electronic properties of silicon that make it a good photocathode has proven difficult. We report the formation of mixed monolayer-functionalized surfaces that incor- porate both methyl and vinylferrocenyl or vinylbipyridyl (vbpy) moieties. The silicon was functionalized using reaction conditions analogous to those of hydrosilylation, but instead of a H-terminated Si surface, a chlorine-terminated Si precursor surface was used to produce the linked vinyl-modified functional group. The functionalized surfaces were characterized by time-resolved photoconductivity decay, X-ray photoelectron spectroscopy (XPS), electro- chemical, and photoelectrochemical measurements. The functionalized Si surfaces were well passivated, exhibited high surface coverage and few remaining reactive Si atop sites, had a very low surface recombination velocity, and displayed little initial surface oxidation. The surfaces were stable toward atmospheric and electrochemical oxidation. The surface coverage of ferrocene or bipyridine was controllably varied from 0 up to 30% of a monolayer without loss of the underlying electronic properties of the silicon. Interfacial charge transfer to the attached ferrocene group was relatively rapid, and a photovoltage of 0.4 V was generated upon illumination of functionalized n-type silicon surfaces in CH₃CN. The immobilized bipyridine ligands bound transition metal ions, and thus enabled the assembly of metal complexes on the silicon surface. XPS studies demonstrated that [Cp∗Rh(vbpy)Cl]Cl, [Cp∗Ir(vbpy)Cl]Cl, and Ru(acac)₂vbpy were assembled on the surface. For the surface prepared with iridium, x-ray absorption spectroscopy at the Ir L_III edge showed an edge energy and post-edge features virtually identical to a powder sample of [Cp∗Ir(bipy)Cl]Cl (bipy is 2,2 ́-bipyridyl). Electrochemical studies on these surfaces confirmed that the assembled complexes were electrochemically active.

直接甲醇燃料电池阳极催化剂及甲醇氧化稀土助催化剂剂研究

燃料电池以其高效、环境友好的发电方式，被誉为21世纪的能源技术。其中，直接甲醇燃料电池（DMFC）更以燃料甲醇来源丰富，价格低廉，储存、携带方便而成为近年的研究热点。但是，DMFC在其实用化之前还需要解决一些重要问题，其中的关键之一就是高性能的贵金属催化剂的研究。我们知道，甲醇的电化学活性要低于氢气三个数量级；而且甲醇在R表面进行电化学氧化时，其中间解离吸附产物会造成贵金属催化剂中毒，显著降低了催化剂的活性。因此，要使DMFC具有相当高的电流密度和运行稳定性，就需要对贵金属催化剂制备进行不断的研究和改进。在本文的工作中，主要从Pt/C催化剂的制备方法、新型碳纳米管载体、稀土助催化剂等三个方面进行了研究和探索，取得的具体结果如下：1．Pt／C催化剂制备方法的研究与改进（1）在本组已有的研究结果基础上，对预沉积还原法进行了一些改进，采用原子吸收光谱（AAS）进行表征，发现Pt的利用率得到了明显的提高。采用X射线衍射。（RD）、透射电子显微镜（TEM）和BET表征铂的粒径、晶态结构和催化剂特性，分析表明，经过改进的预沉积还原法制备的催化剂仍然具有良好的分散性、较小的粒径、较低的晶态结构和良好的催化剂特性，电化学测试证明其性能要优于同等的E-TEK催化剂。（2）借鉴冶金学中的相关技术，提出了一种新的Pt/C催化剂制备方法一程序升温焙烧法。该方法的具体步骤增强了金属催化剂粒子和碳载体之间的相互作用力，提高了碳载体的导电性，并且形成了部分有利于催化反应进行的活性晶态结构。得到的R／C催化剂获得了近似E-TEK催化剂的催化活性，在具体方法上仍有改进的潜力。采用了同（1）的催化剂表征方法。2．甲醇电化学氧化稀土助催化剂研究在直接甲醇燃料电池Pt/C催化剂的研究过程中，一个重要的方面就是助催化剂的研究，并且已经得到了较好的结果。本工作选用了稀土元素为研究对象，因为稀土元素属于过渡金属，具有丰富的d电子轨道，易于和金属形成强的类化学键的吸附作用，并且能够和有机小分子形成多种配位化合物。经过初步的工作，发现了有些稀土离子如Sm3+能够在Pt表面吸附并且对甲醇电化学氧化具有较稳定的促进作用，采用循环伏安法，计时电流，交流阻抗等电化学方法进行了表征。根据实验结果，对其反应机理进行了初步的探讨。3．碳纳米管（CNTs）作为贵金属催化剂载体的研究碳纳米管（CNTs）由于其结构上的特殊性（径向尺寸为纳米量级，轴向尺寸为微米量级）而表现出典型的一维量子材料，同时具有较高的机械强度和超常的电学性能，能够为化学反应提供纳米级的反应场所，因此受到了化学界包括电化学研究人员的极大关注。已经在作为贵金属催化剂载体方面进行了一些研究，本工作的主要内容就是针对Pt/CNTs催化剂对碳纳米管的要求，对其预处理方法进行了改进，采用了如（1）中的催化剂表征方法和（2）中的相关电化学方法进行测定，发现碳纳米管作为贵金属催化剂载体时，对它的纯化处理方法的不同明显地影响了其载体性质和催化剂的活性。

Hydrogen peroxide biosensor based on horseradish peroxidase-Au nanoparticles at viologen grafted glassy carbon electrode

A novel hydrogen peroxide biosensor was fabricated that is based on horseradish peroxidase-Au nanoparticles immobilized on a viologen-modified glassy carbon electrode (GCE) by amino cation radical oxidation in basic solution. The immobilized BAPV acts as a mediator and a covalent linker between GCE and the Au nanoparticles. The biosensor exhibited fast response, good reproducibility, and long-term stability.

Synthesis of carbon nanofibers for mediatorless sensitive detection of NADH

Highly sensitive amperometric detection of dihydronicotinamide adenine dinucleotide (NADH) by using novel synthesized carbon nanofibers (CNFs) without addition of any mediator has been proposed. The CNFs were prepared by combination of electrospinning technique with thermal treatment method and were applied without any oxidation pretreatment to construct the electrochemical sensor. In amperometric detection of NADH, a linear range up to 11.45 mu M with a low detection limit of 20 nM was obtained with the CNF-modified carbon paste electrode (CNF-CPE).

Nonenzymatic glucose sensor based on renewable electrospun Ni nanoparticle-loaded carbon nanofiber paste electrode

A novel nonenzymatic glucose sensor was developed based on the renewable Ni nanoparticle-loaded carbon nanofiber paste (NiCFP) electrode. The NiCF nanocomposite was prepared by combination of electrospinning technique with thermal treatment method. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images showed that large amounts of spherical nanoparticles were well dispersed on the surface or embedded in the carbon nanofibers. And the nanoparticles were composed of Ni and NiO, as revealed by energy dispersive X-ray spectroscopy (EDX) and X-ray powder diffraction (XRD). In application to nonenzymatic glucose determination, the renewable NiCFP electrodes, which were constructed by simply mixing the electrospun nanocomposite with mineral oil, exhibited strong and fast amperometric response without being poisoned by chloride ions. Low detection limit of 1 mu M with wide linear range from 2 mu M to 2.5 mM (R = 0.9997) could be obtained.

Ethanol electrooxidation on Pt/C catalysts promoted with praseodymium oxide nanorods

The Pt/C electrocatalysts containing Pr6O11 nanorods were successfully prepared. By various electrochemical characterization methods, it was demonstrated that the Pr6O11 nanorods have an obviously promotive role for ethanol electrooxidation catalyzed by Pt/C. However, according to the stripping experiment, the promotive effect of Pr6O11 does not result from the easier electrooxidation of the intermediate adsorbate on Pt-Pr6O11/C than on Pt/C. It was supposed that Pr6O11 could promote a certain step in ethanol oxidation, and that the special morphology of the nanorods could further enhance the activity compared with nanoparticles.

A simple route to incorporate redox mediator into carbon nanotubes/Nafion composite film and its application to determine NADH at low potential

Through a new and simple ion-exchange route, two-electron redox mediator thionine has been deliberately incorporated into the carbon nanotubes (CNTs)/Nafion composite film due to the fact that there is strong interaction between any of two among the three materials (ion-exchange process between thionine and Nafion, strong adsorption of thionine by CNTs, and wrapping and solubilizing of CNTs with Nation). The good homogenization of electron conductor CNTs in the integrated films provides the possibility of three-dimensional electron conductive network. The resulting integrated films exhibited high and stable electrocatalytic activity toward NADH oxidation with the significant decrease of high overpotential, which responds more sensitively more than those modified by thioine or CNTs alone. Such high electrocatalytic activity facilitated the low potential determination of NADH (as low as -0.1 V), which eliminated the interferences from other easily oxidizable species. In a word, the immobilization approach is very simple, timesaving and effective, which could be extended to the immobilization of other cationic redox mediators into the CNTs/Nafion composite film. And these features may offer potential promise for the design of amperometric biosensors.

Assembly of 12-tungstosilicic acid and 4-aminobenzo-15-crown-5 ether based on the electrostatic attraction through bridging of oxonium ions on different substrates

Based on the electrostatic attraction Keggin-type polyoxometalate H4SiW12O40 (SiW12) and small molecule 4-aminobenzo-15-crown-5 ether (4-AB15C5) were alternately deposited on poly (allylamine hydrochloride) (PAH)-derived indium tin oxide (ITO) substrate through a layer-by-layer (LBL) self-assembly, forming a supramolecular multilayer film (film-A). SiW12 was also deposited on a glassy carbon electrode (GCE) derived by 4-AB15C5 via covalent bonding in 0.1 M NaCl aqueous solution and formed a composite monolayer film (film-B). UV-vis absorption spectroscopy, X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared (FTIR) spectroscopy measurements demonstrated that the interactions between SiW12 and 4-AB15C5 in both two film electrodes were the same and caused by the bridging action of oxonium ions. But, the nanostructure in the two film electrodes was different. 4-AB15C5 in film-A was oriented horizontally to ITO substrate, however, that in film-B was oriented vertically to GCE. Namely film-A corresponded to a layer structure, and film-B corresponded to an intercalation structure.

Enhancement of the electrooxidation of ethanol on Pt-Sn-P/C catalysts prepared by chemical deposition process

In this paper, five Pt3Sn1/C catalysts have been prepared using three different methods. It was found that phosphorus deposited on the surface of carbon with Pt and Sn when sodium hypophosphite was used as reducing agent by optimization of synthetic conditions such as pH in the synthetic solution and temperature. The deposition of phosphorus should be effective on the size reduction and markedly reduces PtSn nanoparticle size, and raise electrochemical active surface (EAS) area of catalyst and improve the catalytic performance. TEM images show PtSnP nanoparticles are highly dispersed on the carbon surface with average diameters of 2 nm. The optimum composition is Pt3Sn1P2/C (note PtSn/C-3) catalyst in my work. With this composition, it shows very high activity for the electrooxidation of ethanol and exhibit enhanced performance compared with other two Pt3Sn1/C catalysts that prepared using ethylene glycol reduction method (note PtSn/C-EG) and borohydride reduction method (note PtSn/-B). The maximum power densities of direct ethanol fuel cell (DEFC) were 61 mW cm(-2) that is 150 and 170% higher than that of the PtSn/C-EG and PtSn/C-B catalyst.

Modification of electrode surface through electrospinning followed by self-assembly multilayer film of polyoxometalate and its photochromic

Electrospun poly (vinyl alcohol) (PVA) nanofibers mat was collected on indium tin oxide (ITO) substrate. Heat crosslinked nanofibers mat became water-insoluble and firmly fixed on ITO substrate even in water. Oppositely charged poly (allylamine hydrochloride) (PAH) and Dawson-type polyoxometalate (POM), Na6P2Mo18O62 (P2Mo18), were alternately assembled on PVA nanofibers-coated ITO substrate to construct multilayer film through an electrostatic layer-by-layer (LBL) technique. The scanning electron microscope (SEM) images showed that P2Mo18 multilayer film was selectively deposited on PVA nanofibers while the unoccupied space by nanofibers on bare ITO was acted as substrate at the same time because the electrospun nanofibers have larger surface area and surface energy than the flat substrate. The cyclic voltammograms current responses of the P2Mo18 multilayer film on PVA/ITO electrode showed three well-defined redox couples of P2Mo18, but very small because P2Mo18 multilayer film was selectively deposited on PVA nanofibers with poor conductivity. In addition, the photochromic behavior of P2Mo18 multilayer film on PVA/ITO was investigated through UV-vis spectra and electron spin resonance (ESR). Fourier-transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) proved that the charge-transfer complex was formed between PAH and P2Mo18 after UV irradiation.

Studies of interaction between iron (III) and intermediates of synthetic neuromelanin by means of cyclic voltammetry of Fe(CN)(3-)(6) and dopamine

Neuromelanin is a complex polymer pigment found primarily in the dopaminergic neurons of the human substantia nigra, whose composition is complex including production of dopamine auto-oxidation, glutathione and a variety of amino acid. Neuromelanin forms stable complex with iron (111). We observed that 5,6-dihydroxyindole and its ramification possessed strong ability of chelating iron (111), and they are the production of dopamine auto-oxidation under physiological pH condition. In the present Of L-Cysteine, the relative yields of electrochemical oxidation of dopamine also had strong ability of chelating iron (111). The experimental results suggest that 5,6-dihydroxyindole and 5-S-cysteineldopamine play important roles in the process of synthetic neuromelanin chelating iron (111).

Toluidine blue modified self-assembled silica gel coated gold electrode as biosensor for NADH

A toluidine blue modified gold electrode was constructed using self-assembled silica gel technique. Firstly, toluidine blue was encapsulated within 3D network of silica self-assembly monolayer on the surface of gold electrode. Secondly, another layer of silica sol was further assembled to protect from leaching of mediator or possible contamination. The electrochemical characteristics of toluidine blue immobilized within self-assembled silica gel were studied in detail. The modified electrode was applied for electrochemical oxidation of NADH with satisfactory results.

Carbon ceramic electrodes modified with sub-micron particles of new methylene blue (NMB) intercalated alpha-zirconium phosphate

New methylene blue-intercalated a-zirconium phosphate (NMBZrP) was synthesized in the presence of n-butylamine and characterized by powder XRD, FTIR, TEM and elemental analysis. Sub-micron particles of NMBZrP in deionized water were apt to deposit onto the surface of graphite powder to yield graphite powder-supported NMBZrP, which was subsequently dispersed into methyltrimethoxysilane-derived gels to fabricate surface-renewable, stable, rigid carbon ceramic electrodes containing new methylene blue. Cyclic voltammetric studies revealed that peak currents of the NMBZrP-modified electrode were surface-confined at low scan rates but diffusion-controlled. at high scan rates. In addition, NMBZrP immobilized in a carbon ceramic matrix presented a two-electron, three-proton redox process in acidic aqueous solution in the pH range from 0.52 to 3.95.