In situ Hydrothermal Oxidation of Ternary FeCoNi Alloy Electrode for Overall Water Splitting

Exploring noble metal-free catalyst materials for high efficient electrochemical water splitting to produce hydrogen is strongly desired for renewable energy development.In this article,a novel bifunctional catalytic electrode of insitu-grown type for alkaline water splitting based on FeCoNi alloy substrate has been successfully prepared via a facile one-step hydrothermal oxidation route in an alkaline hydrogen peroxide medium.It shows that the matrix alloy with the atom ratio 4∶3∶3 of Fe∶Co∶Ni can obtain the best catalytic performance when hydrothermally treated at 180℃for 18 h in the solution containing 1.8 M hydrogen peroxide and 3.6 M sodium hydroxide.The as-prepared Fe_(0.4)Co_(0.3)Ni_(0.3)-1.8 electrode exhibits small overpotentials of only 184 and 175 mV at electrolysis current density of 10 mA cm^(-2)for alkaline OER and HER processes,respectively.The overall water splitting at electrolysis current density of 10 mA cm^(-2)can be stably delivered at a low cell voltage of 1.62 V.These characteristics including the large specific surface area,the high surface nickel content,the abundant catalyst species,the balanced distribution between bivalent and trivalent metal ions,and the strong binding of in-situ naturally growed catalytic layer to matrix are responsible for the prominent catalytic performance of the Fe_(0.4)Co_(0.3)Ni_(0.3)-1.8 electrode,which can act as a possible replacement for expensive noble metal-based materials.

Promoting effects of Fe_2O_3 to Pt electrocatalysts toward methanol oxidation reaction in alkaline electrolyte

Fe_2O_3 nanorods and hexagonal nanoplates were synthesized and used as the promoters for Pt electrocatalysts toward the methanol oxidation reaction（MOR） in an alkaline electrolyte.The catalysts were characterized by scanning electron microscopy,transmission electron microscopy,X-ray diffraction,X-ray photoelectron spectroscopy,cyclic voltammetry and chronoamperometry.The results show that the presence of Fe_2O_3 in the electrocatalysts can promote the kinetic processes of MOR on Pt,and this promoting effect is related to the morphology of the Fe_2O_3 promoter.The catalyst with Fe_2O_3 nanorods as the promoter（Pt-Fe_2O_3/C-R） exhibits much higher catalytic activity and stability than that with Fe_2O_3 nanoplates as the promoter（Pt-Fe_2O_3/C-P）.The mass activity and specific activity of Pt in a Pt-Fe_2O_3/C-R catalyst are 5.32 A/mgpt and 162.7 A/m^2_（Pt）,respectively,which are approximately 1.67 and 2.04 times those of the Pt-Fe_2O_3/C-P catalyst,and 4.19 and 6.16 times those of a commercial PtRu/C catalyst,respectively.Synergistic effects between Fe_2O_3 and Pt and the high content of Pt oxides in the catalysts are responsible for the improvement.These findings contribute not only to our understanding of the MOR mechanism but also to the development of advanced electrocatalysts with high catalytic properties for direct methanol fuel cells.

Determination of Lignin in Marine Sediment Using Alkaline Cupric Oxide Oxidation-Solid Phase Extraction-on-Column Derivatization-Gas Chromatography

Lignin serves as one of the most important molecular fossils for tracing Terrestrial Organic Matters （TOMs） in marine environment. Extraction and derivatization of lignin oxidation products （LOPs） are crucial for accurate quantification of lignin in marine sediment. Here we report a modification of the conventional alkaline cupric oxide （CuO） oxidation method, the modification consisting in a solid phase extraction （SPE） and a novel on-column derivatization being employed for better efficiency and reproducibility. In spiking blanks, recoveries with SPE for the LOPs are between 77.84% and 99.57% with relative standard deviations （RSDs） ranging from 0.57% to 8.04% （n=3）, while those with traditional liquid-liquid extraction （LLE） are from 44.52% to 86.16% With RSDs being from 0.53% to 13.14% （n=3）. Moreover, the reproducibility is greatly improved with SPE, with less solvent consumption and shorter processing time. The average efficiency of on-column derivatization for LOPs is 100.8%±0.68%, which is significantly higher than those of in-vial or in-syringe derivatization, thus resulting in still less consumption of derivatizing reagents.Lignin in the surface sediments sampled from the south of Yangtze River estuary, China, was determined with the established method. Recoveries of 72.66% to 85.99% with standard deviation less than 0.01mg/10g dry weight are obtained except for p-hydroxybenzaldehyde. The lignin content ∑8 （produced from 10g dry sediment） in the research area is between 0.231 and 0.587mg. S/V and C/V ratios （1.028 ± 0.433 and 0.192±0.066, respectively） indicate that the TOMs in this region are originated from a mixture of woody and nonwoody angiosperm plants; the high values or （Ad/Al）v suggest that the TOMs has been highly degraded.

Ni(OH)_2-Ni/C for hydrogen oxidation reaction in alkaline media

The development of the hydrogen electrode is vital for the application of alkaline polymer electrolyte fuel cells(APEFCs).In this study,a series of Ni(OH)_2 decorated Ni/C catalysts(Ni(OH)_2-Ni/C) were prepared by a three-step electrochemical treatment of Ni/C.The existence of Ni(OH)_2 was demonstrated by X-ray photoelectron spectroscopy(XPS),and the surface molar ratio of Ni(OH)_2/Ni of the samples was estimated via an electrochemical method.The HOR catalytic activity of the catalysts was evaluated by a rotation disk electrode(RDE) method,and a "volcano plot" was established between the HOR exchange current(j0) and the surface molar ratio of Ni(OH)_2/Ni.On top of the "volcano",the surface molar ratio of Ni(OH)_2/Ni is1.1:1,the j0 of which was 6.8 times of that of Ni/C.The stability of the samples toward HOR was evaluated to be good.Our study added a systematic experimental evidence to the HOR research,showing that the HOR catalytic activity of Ni can be deliberately controlled via decoration of Ni(OH)_2,which may help understanding the HOR mechanism on Ni.

Improved hydrogen oxidation reaction under alkaline conditions by Au–Pt alloy nanoparticles

This work demonstrates the outstanding performance of alloyed Au1 Pt1 nanoparticles on hydrogen oxidation reaction(HOR)in alkaline solution.Due to the weakened hydrogen binding energy caused by uniform incorporation of Au,the alloyed Au1Pt1/C nanoparticles exhibit superior HOR activity than commercial PtRu/C.On the contrary,the catalytic performance of the phase-segregated Au2Pt1/C and Au1Pt1/C bimetallic nanoparticles in HOR is significantly worse.Moreover,Au1Pt1/C shows a remarkable durability with activity dropping only 4% after 3000 CV cycles,while performance attenuation of commercial PtRu/C is high up to 15% under the same condition.Our results indicate that the alloyed Au1Pt1/C is a promising candidate to substitute commercial PtRu/C for hydrogen oxidation reaction in alkaline electrolyte.

Platinum nanoparticles coated by graphene layers: A low-metal loading catalyst for methanol oxidation in alkaline media

Platinum catalysts play a major role in the large scale commercialization of direct methanol fuel cells(DMFC).Here,we present a procedure to create a nanostructural graphene-platinum(Gr Pt)composite containing a small amount(5.3 wt%)of platinum nanoparticles coated with at least four layers of graphene.The composite,as Gr Pt ink,was deposited on a glassy carbon electrode and its electrocatalytic activity in a methanol oxidation reaction(MOR)was evaluated in a 1 M CH3OH/1 M NaOH solution.The results indicated an enhanced catalytic performance of GrPt towards MOR in alkaline media compared with the Pt/C material.Electron energy-loss spectroscopy and X-ray photoelectron spectroscopy(recorded before and after the electrochemical assays)were employed to analyze the changes in the chemical composition of the nanomaterial and to explain the transformations that took place at the electrode surface.Our findings suggest that growing of graphene on platinum nanoparticles improve the catalytic performance of platinum-graphene composites towards MOR in alkaline media.

Oxidation of propane to acrylic acid and acetic acid over alkaline earth-doped Mo-V-Sb-O_x catalysts

Alkaline earth metal （Mg,Ca,Sr and Ba）-doped Mo-V-Sb-O x catalysts,prepared by a dry-up method,have been investigated for their catalytic performance in the oxidation of propane under different reaction conditions.The catalysts have been characterized by N2 adsorption-desorption,temperature-programmed desorption （TPD） of NH3,SEM and XRD.Influence of water vapor on the catalytic performance,particularly on the selectivities to acetic acid and acrylic acid,has also been studied.The selectivity to acrylic acid was improved significantly by the doping of alkaline earth metals to Mo-V-Sb-O x catalysts.The surface acidic sites of the catalyst decreased with the doping of the catalyst with alkaline earth metals,which ultimately was found to be beneficial for obtaining high selectivity to acrylic acid.The catalytic activity and product selectivities were found to be influenced by the reaction temperature,C3H8/O2 ratio and space velocity.A significant improvement in the selectivity to acrylic acid has also been observed by the addition of water vapor in the feed of propane and oxygen in the oxidation of propane.

Recent advances in alkaline hydrogen oxidation reaction

The development of highly efficient electrocatalysts toward hydrogen oxidation reaction(HOR)under alkaline media is essential for the commercialization of alkaline exchange membrane fuel cells(AEMFCs).However,the HOR kinetics in alkaline is two to three orders of magnitude slower than that in acid.More critically,fundamental understanding of the sluggish kinetics derived from the p H effect is still debatable.In this review,the recent development of understanding HOR mechanism and rational design of advanced HOR electrocatalysts are summarized.First,recent advances in the theories focusing on fundamental understandings of HOR under alkaline electrolyte are comprehensively discussed.Then,from the aspect of intermediates binding energy,optimizing hydrogen binding energy(HBE)and increasing hydroxyl binding energy(OHBE),the strategies for designing efficient alkaline HOR catalysts are summarized.At last,perspectives for the future research on alkaline HOR are pointed out.

Methanol oxidation in acidic and alkaline electrolytes using PtRuIn/C electrocatalysts prepared by borohydride reduction process

PtRuIn/C electrocatalysts( 20% metal loading by weight) were prepared by sodium borohydride reduction process using H_2PtCl6·6H_2O,RuCl_3·xH_2O and InCl_3·xH_2O as metal sources,borohydride as reducing agent and Carbon Vulcan XC72 as support. The synthetized PtRuIn/C electrocatalysts were characterized by X-ray diffraction( XRD),energy dispersive analysis( EDX),transmission electron microscopy( TEM),cyclic voltammetry( CV),chronoamperommetry( CA) and polarization curves in alkaline and acidic electrolytes( single cell experiments). The XRD patterns showPtpeaks are attributed to the face-centered cubic( fcc) structure,and a shift of Pt( fcc) peaks indicates that Ru or In is incorporated into Ptlattice. TEMmicrographs showmetal nanoparticles with an average nanoparticle size between 2.7 and 3.5 nm. Methanol oxidation in acidic and alkaline electrolytes was investigated at room temperature,by CV and CA. PtRu/C( 50 ∶ 50) shows the highest activity among all electrocatalysts in study considering methanol oxidation for acidic and alkaline electrolyte. Polarization curves at 80 ℃ showPtRuIn/C( 50 ∶ 25 ∶ 25)with superior performance for methanol oxidation,when compared to Pt/C,PtIn/C and PtRu/C for both electrolytes. The best performance obtained by PtRuIn/C( 50 ∶ 25 ∶ 25) in real conditions could be associated with the increased kinetics reaction and/or with the occurrence simultaneously of the bifunctional mechanism and electronic effect resulting from the presence of Ptalloy.

NO_x Removal by Oxidation on Alumina Supported Metal Oxide Catalysts Followed by Alkaline Absorption

NO oxidation is the key reaction for the oxidative NO x removal process.In this work,the catalytic NO oxidation performance of the Al2O3 supported metal oxide catalysts(M-Al2O3,M=V,Mn,Fe,Co,Ni and Ce)is evaluated.The oxidation product is absorbed by the alkaline solution for NO x removal.The NO oxidation activity increases in the following order:V<<Ce<Ni<Fe<Co<Mn.As the NO oxidation involves the O uptake into the metal oxide lattice and oxidation of the adsorbed NO by the lattice O,the highest activity of Mn is attributed to the appropriate redox potential of Mn,which favors both the O uptake and the NO oxidation steps.For all the M-Al2O3 catalysts,there is an intermediate temperature to achieve maximum NO conversion,which is lower for more efficient M-Al2O3 catalyst.The temperature dependence suggests that the NO oxidation at low temperature is kinetically controlled while it is thermodynamically limited at higher temperature.The NO x removal ratio by the alkaline solution absorption increases with the NO2/NO ratio,with a maximum removal ratio of 80%when the NO2/NO ratio is higher than 3,indicating that a very high NO conversion is unnecessary.

Laser-Induced Single Event Transients in Local Oxidation of Silicon and Deep Trench Isolation Silicon-Germanium Heterojunction Bipolar Transistors

We present a study on the single event transient （SET） induced by a pulsed laser in different silicon-germanium （SiGe） heterojunction bipolar transistors （HBTs） with the structure of local oxidation of silicon （LOCOS） and deep trench isolation （DTI）. The experimental results are discussed in detail and it is demonstrated that a SiGe HBT with the structure of LOCOS is more sensitive than the DTI SiGe HBT in the SET. Because of the limitation of the DTI structure, the charge collection of diffusion in the DTI SiGe HBT is less than that of the LOCOS SiGe HBT. The SET sensitive area of the LOCOS SiGe HBT is located in the eollector-substrate （C/S） junction, while the sensitive area of the DTI SiGe HBT is located near to the collector electrodes.

Additive effects of alkaline-earth metals and nickel on the performance of Co/γ-Al_2O_3 in methane catalytic partial oxidation

Nano-sized γ-alumina （γ-Al2O3） was first prepared by a precipitation method. Then, active component of cobalt and a series of alkaline- earth metal promoters or nickel （Ni） with different contents were loaded on the γ-Al2O3 support. The catalysts were characterized by N2 adsorption-desorption, X-ray diffraction （XRD） and thermogravimetry analysis （TGA）. The activity and selectivity of the catalysts in catalytic partial oxidation （CPO） of methane have been compared with Co/γ-Al2O3, and it is found that the catalytic activity, selectivity, and stability are enhanced by the addition of alkaline-earth metals and nickel. The optimal loadings of strontium （Sr） and Ni were 6 and 4 wt%, respectively. This finding will be helpful in designing the trimetallic Co-Ni-Sr/γ-Al2O3 catalysts with high performance in CPO of methane

A novel on-line electrochemical transmission infrared spectroscopy to study the current efficiency of carbonates for ethanol oxidation reactions in alkaline media

Research on the reaction mechanism of ethanol oxidation reaction(EOR) is important for the development of highly active EOR electro-catalysts. One of the main difficulties in the EOR study is the quantitative analysis of the non-volatile products. Conventional on-line electrochemical flowing transmission infrared spectroscopy(ETIRS) can only collect a part of the carbonate products of EOR in alkaline media, making the further quantitative study impossible. Herein, a new ETIRS system has been designed and prepared by employing a cation-exchange membrane(Nafion) in the sampling hood. The using of the Nafion membrane can prevent the anions crossing over by confining the generated carbonates in the sampling hood without diffusing into the bulk electrolyte. Therefore, the collection efficiency of the carbonate products as well as the test accuracy of the carbonate current efficiency has been significantly improved. The result of CO stripping reaction shows that ca. 100% of the carbonate product is able to be collected in alkaline media by this new system. The influence of the experimental temperature to the carbonate current efficiency has been further studied on Pt/C toward EOR in alkaline media.

Enhancing hydrogen electrocatalytic oxidation on Ni_(3)N/MoO_(2)in-plane heterostructures in alkaline solution

Nickel(Ni)-based materials act as one of the most promising candidates as platinum-group-metal-free(PGM-free)electrocatalysts for hydrogen oxidation reaction(HOR)in alkaline solution.Nevertheless,the electrocatalytic activity of pure Ni is significantly limited due to the sluggish kinetics under alkaline condition.To accelerate the kinetics,constructing heterostructures and nitride structures have been developed as two representative strategies.Here,we combined the two methods and presented a facile synthesis of the sheet-like Ni_(3)N/MoO_(2)in-plane heterostructures for enhanced HOR in alkaline electrolytes.Relative to Ni or Ni_(3)N,the Ni_(3)N/MoO_(2)in-plane heterostructures exhibited a significantly increased mass activity by 8.6-fold or 4.4-fold,respectively.Mechanistic studies revealed that the enhanced activity of Ni_(3)N/MoO_(2)could be attributed to the weakened hydrogen adsorption and strengthened hydroxyl adsorption.This work provides a facile approach to design high-efficiency catalysts for hydrogen-oxidation catalysis and beyond.

Electrocatalysts development for hydrogen oxidation reaction in alkaline media:From mechanism understanding to materials design

Anion exchange membrane(AEM)fuel cells have gained great attention partially due to the advantage of using non-precious metal as catalysts.However,the reaction kinetics of hydrogen oxidation reaction(HOR)is two orders of magnitude slower in alkaline systems than in acid.To understand the slower kinetics of HOR in base,two major theories have been proposed,such as(1)pH dependent hydrogen binding energy as a major descriptor for HOR;and(2)bifunctional theory based on the contributions of both hydrogen and hydroxide adsorption for HOR in alkaline electrolyte.Here,we discuss the possible HOR mechanisms in alkaline electrolytes with the corresponding change in their Tafel behavior.Apart from the traditional Tafel-Volmer and Heyrovsky-Volmer HOR mechanisms,the recently proposed hydroxide adsorption step is also discussed to illustrate the difference in HOR mechanisms in acid and base.We further summarize the representative works of alkaline HOR catalyst design(e.g.,precious metals,alloy,intermetallic materials,Ni-based alloys,carbides,nitrides,etc.),and briefly describe their fundamental HOR reaction mechanism to emphasize the difference in elementary reaction steps in alkaline medium.The strategy of strengthening local interaction that facilitates both H2 desorption and Hads+OHads recombination is finally proposed for future HOR catalyst design in alkaline environment.

Study on TEMPO-Mediated Selective Oxidation of Alkaline Natural Cellulose Pulp and Properties of Its Products

It has been reported that natural cellulose （cellulose I） can not be oxidized by TEMPO - NaOCI - NaBr system, one of TEMPO-mediated selective oxidant systems, but regenerated cellulose （cellulose Ⅱ ） can be completely selectively oxidized. In the present work, natural cellulose pulp was treated with NaOH solution, which concentration is lower than 20 wt%. The alkaline celluloses obtained were oxidized by TEMPO - NaOCI - NaBr system and the factors which influence the selective oxidation reaction rate have been investigated. The structure of the oxidized products has been characterized by Fourier transform-infrared （FTIR）, nuclear magenatic resonace （NMR） and wide angle X-ray diffraction （WAXD） methods, and their adsorption properties for Cu^2＋ and Cd^2＋ in aqueous solutions have been preliminarily examined. The results show that after the alkaline treatment, the primary hydroxyl at C6 position of natural cellulose can be selectively oxidized to carboxyl group in the reaction medium at pH 10.8, the oxidation rate becomes greater with the NaOH concentration and alkaline treatment time increasing. The alkaline treatment has a great effect on the crystal structure of natural cellulose, but the crystal structure of alkaline cellulose keeps almost unchanged after oxidation. The adsorption capacity is enhanced by introducing carboxyl groups into the cellulose macromolecular chains.

Electro-oxidation of mixed reactants of ethanol and formate on Pd/C in alkaline fuel cells

Direct ethanol fuel cells have attracted attention as an alternative energy technology due to several advantages such as high theoretical energy density and abundant supply of ethanol.In spite of the advantages,commercialization of direct ethanol fuel cells is hampered by the relatively low performance caused by its slow oxidation kinetics and difficulty of complete oxidation.In this study,formate,which has relatively faster oxidation kinetics,was mixed with ethanol to compensate the latter’s sluggish kinetics.Effects of p H,concentration,scan rate,and temperature on the mixed reactants oxidation on Pd were investigated by electrochemical experiments such as potential sweep and potentiostatic methods.Furthermore,the potential of the mixed reactants as fuel was evaluated by single cell experiments.As a result,we demonstrate that mixing formate with ethanol results in enhanced power performance in a single cell system.

Selective recovery of lead from zinc oxide dust with alkaline Na_2EDTA solution

The selective recovery of lead from the zinc oxide dust using an alkaline Na2EDTA solution was investigated. The effects of temperature, leaching time, Na2EDTA concentration and initial NaOH concentration on the leaching rates of lead and zinc were studied. The following optimized leaching conditions were obtained： liquid-to-solid ratio 5：1 mL/g, stirring speed 650 r/min, Na2EDTA concentration 0.12 mol/L, initial NaOH concentration 0.5 mol/L, leaching temperature 70 ℃, leaching time 120 min. Under the optimized conditions, the average leaching rates of lead, zinc, fluoride and chloride are 89.92%, 0.94%, 62.84% and 90.02%, respectively. The filtrate was used to electrowin lead powders. The average current efficiency of electrowinning is about 93% and lead content is higher than 98% under the conditions of temperature of 60 ℃, current density of 200 A/m2, H3PO4 concentration of 1.5 g/L, and lead ion concentration of above 5 g/L. The consumption of Na2EDTA and the direct current are about respectively 0.218 kg and 0.958 kW·h for per kilogram of lead powder.

Study on rare earth/alkaline earth oxide-doped CeO_2 solid electrolyte

Five types of rare earth/alkaline earth oxide-doped CeO2 superfine-powders were synthesized by a low-temperature combustion technique. The relevant solid electrolyte materials were also sintered by pressureless sintering at different temperatures. The results of X-ray diffraction and transmission electron microscopy showed that the grain size of the powders was approximately 20-30 nm, and rare earth/alkaline earth oxides were completely dissolved into ceria-based solid solution with fluorite structure. The electrical conductivities of the SmzO3-CeO2 system were measured by the ac impedance technique in air at temperatures ranging from 513-900℃. The results indicated that the ionic conductivities of Srno.2oCe0.8Ol.875 solid electrolyte increase with increasing sintering temperature, and the relationship between the conductivities and measuring temperature obeys the An＇henius equation. Then the SmzO3-CeO2 material was further doped with other rare earth/alkaline earth oxide, and the conductivities improve with the effective index.

Effect of Various Alkaline Oxides on Broadband Near-infrared Luminescence from Bismuth-Doped Muminophosphate Glasses

We reported effect of various alkaline oxides on the broadband infrared luminescence from bismuth-doped aluminophosphate glasses. The samples of （99-x）P2O3-17Al2O3-xR2O-IBi2O3 （R=Li, Na and K, x=0 and 10 in mol%） were prepared under reducing condition controlled by additional carbon powders. The fluorescent intensity decreased with increasing content of alkaline oxides and basicity of host glasses. The 1/e fluorescence lifetime of the 72P2O3-17Al2O3-10R2O-1Bi2O3 （R=Li, Na and K） glasses decreased from 461 to 316 μs, as alkaline ions changed from Li^＋ to K^＋.