Discrete formulation of mixed finite element methods for vapor deposition chemical reaction equations

The vapor deposition chemical reaction processes, which are of extremely extensive applications, can be classified as a mathematical model by the following governing nonlinear partial differential equations containing velocity vector, temperature field, pressure field, and gas mass field. The mixed finite element （MFE） method is employed to study the system of equations for the vapor deposition chemical reaction processes. The semidiscrete and fully discrete MFE formulations are derived. And the existence and convergence （error estimate） of the semidiscrete and fully discrete MFE solutions are demonstrated. By employing MFE method to treat the system of equations for the vapor deposition chemical reaction processes, the numerical solutions of the velocity vector, the temperature field, the pressure field, and the gas mass field can be found out simultaneously. Thus, these researches are not only of important theoretical means, but also of extremely extensive applied vistas.

Chemical Vapor Deposition Mechanism of Copper Films on Silicon Substrates

A versatile metal-organic chemical vapor deposition （MOCVD） system was designed and constructed. Copper films were deposited on silicon （100） substrates by chemical vapor deposition （CVD） using Cu（hfac）2 as a precursor. The growth of Cu nucleus on silicon substrates by H2 reduction of Cu（hfac）2 was studied by atomic force microscopy and scanning electron microscopy. The growth mode of Cu nucleus is initially Volmer-Weber mode （island）, and then transforms to Stranski-Rastanov mode （layer-by-layer plus island）. The mechanism of Cu nucleation on silicon （100） substrates was further investigated by X-ray photoelectron spectroscopy. From Cu2p, O1s, F1s, Si2p patterns, the observed C=O, OH and CF3/CF2 should belong to Cu（hfac） formed by the thermal dissociation of Cu（hfac）2. H2 reacts with hfac on the surface, producing OH. With its accumulation, OH reacts with hfac, forming HO-hfac, and desorbs, meanwhile, the copper oxide is reduced, and thus the redox reaction between Cu（hafc）2 and H2 occurs.

Effective exposure of nitrogen heteroatoms in 3D porous graphene framework for oxygen reduction reaction and lithium–sulfur batteries

The introduction of nitrogen heteroatoms into carbon materials is a facile and efficient strategy to regulate their reactivities and facilitate their potential applications in energy conversion and storage. However,most of nitrogen heteroatoms are doped into the bulk phase of carbon without site selectivity, which significantly reduces the contacts of feedstocks with the active dopants in a conductive scaffold. Herein we proposed the chemical vapor deposition of a nitrogen-doped graphene skin on the 3D porous graphene framework and donated the carbon/carbon composite as surface N-doped grapheme（SNG）. In contrast with routine N-doped graphene framework（NGF） with bulk distribution of N heteroatoms, the SNG renders a high surface N content of 1.81 at%, enhanced electrical conductivity of 31 S cm^（-1）, a large surface area of 1531 m^2 g^（-1）, a low defect density with a low I_D/I_G ratio of 1.55 calculated from Raman spectrum, and a high oxidation peak of 532.7 ℃ in oxygen atmosphere. The selective distribution of N heteroatoms on the surface of SNG affords the effective exposure of active sites at the interfaces of the electrode/electrolyte, so that more N heteroatoms are able to contact with oxygen feedstocks in oxygen reduction reaction or serve as polysulfide anchoring sites to retard the shuttle of polysulfides in a lithium–sulfur battery. This work opens a fresh viewpoint on the manipulation of active site distribution in a conductive scaffolds for multi-electron redox reaction based energy conversion and storage.

Promoting effect of nitrogen doping on carbon nanotube-supported RuO2 applied in the electrocatalytic oxygen evolution reaction

RuO2 nanoparticles supported on multi-walled carbon nanotubes（CNTs） functionalized with oxygen（OCNTs） and nitrogen（NCNTs） were employed for the oxygen evolution reaction（OER） in 0.1 M KOH.The catalysts were synthesized by metal-organic chemical vapor deposition using ruthenium carbonyl（Ru3（CO）（12）） as Ru precursor. The obtained RuO2/OCNT and RuO2/NCNT composites were characterized using TEM, H2-TPR, XRD and XPS in order probe structure–activity correlations, particularly, the effect of the different surface functional groups on the electrochemical OER performance. The electrocatalytic activity and stability of the catalysts with mean RuO2 particle sizes of 13–14 nm was evaluated by linear sweep voltammetry, cyclic voltammetry, and chronopotentiometry, showing that the generation of nitrogen-containing functional groups on CNTs was beneficial for both OER activity and stability. In the presence of RuO2, carbon corrosion was found to be significantly less severe.

C-dots assisted synthesis of gold nanoparticles as labels to catalyze copper deposition for ultrasensitive electrochemical sensing of proteins

We report an ultrasensitive protocol for electrochemical sensing using the hydroxyl-rich C-dots assisted synthesis of gold nanoparticles(C-dots@AuNP) as labels with copper depositon reaction. The C-dots catalyzing copper deposition reaction was implemented for the first time. We constructed a sandwich-type immunosensor on the chitosan modified glassy carbon electrode(GCE) by glutaraldehyde(GA) crosslinking, with C-dots@AuNP as biolabels. Copper was deposited on the catalytic surfaces of second antibody-conjugated C-dots@AuNP nanoparticles through CuSO_4-ascorbic acid reduction, because both C-dots and AuNPs could strongly catalyze the CuSO_4 and ascorbic acid to form Cu particles, which amplified the detection signal. Then the corresponding antigen was quantified based on simultaneous chemical-dissolution/cathodic-preconcentration of copper for insitu analysis using anodic stripping square wave voltammetry(ASSWV) directly on the modified electrode. Under optimized conditions, these electrodes were employed for sandwich-type immunoanaly sis, pushing the lower limits of detection(LODs)down to the fg mL^(-1) level for human immunoglobulin G(IgG) and cardiac troponin I(cTnI), a cardiac biomarker. These novel sensors have good stability and acceptable accuracy and reproducibility, suggesting potential applications in clinical diagnostics.

Selective oxidation of methane and carbon deposition over Fe_2O_3/Ce_(1-x)Zr_xO_2 oxides

A series of Fe2O3/Al2O3, Fe2O3/CeO2, Ce0.7Zr0.3O2, and Fe2O3/Ce1-xZrxO2（x = 0.1–0.4） oxides was prepared and their physicochemical features were investigated by X-ray diffraction（XRD）, transmission electron microscope（TEM）, and H2-temperature-programmed reduction（H2-TPR） techniques. The gas–solid reactions between these oxides and methane for syngas generation as well as the catalytic performance for selective oxidation of carbon deposition in O2-enriched atmosphere were investigated in detail. The results show that the samples with the presence of Fe2O3show much higher activity for methane oxidation compared with the Ce0.7Zr0.3O2solid solution,while the CeO2-contained samples represent higher CO selectively in methane oxidation than the Fe2O3/Al2O3sample. This suggests that the iron species should be the active sites for methane activation, and the cerium oxides provide the oxygen source for the selective oxidation of the activated methane to syngas during the reaction between methane and Fe2O3/Ce0.7Zr0.3O2. For the oxidation process of the carbon deposition, the CeO2-containing samples show much higher CO selectivity than the Fe2O3/Al2O3sample, which indicates that the cerium species should play a very important role in catalyzing the carbon selective oxidation to CO. The presence of the Ce–Zr–O solid solution could induce the growth direction of the carbonfilament, resulting in a loose contact between the carbon filament and the catalyst. This results in abundant exposed active sites for catalyzing carbon oxidation, strongly improving the oxidation rate of the carbon deposition over this sample. In addition, the Fe2O3/Ce0.7Zr0.3O2also represents much higher selectivity（ca. 97 %） for the conversion of carbon to CO than the Fe2O3/CeO2sample, which can be attributed to the higher concentration of reduced cerium sites on this sample. The increase of the Zr content in the Fe2O3/Ce1-xZrxO2samples could improve the reactivity of the materials for methane oxidation, but it also reduces the selectivity for CO formation.

BiVO_4 semiconductor sensitized solar cells

Semiconductor sensitized solar cells(SSSCs) are promising candidates for the third generation of cost-effective photovoltaic solar cells and it is important to develop a group of robust, environment-friendly and visible-light-responsive semiconductor sensitizers. In this paper, we first synthesized bismuth vanadate(Bi VO4) quantum dots by employing facile successive ionic layer adsorption and reaction(SILAR) deposition technique, which we then used as a sensitizer for solar energy conversion. The preliminary optimised oxide SSSC showed an efficiency of 0.36%, nearly 2 orders of magnitude enhancement compared with bare Ti O2, due to the narrow bandgap absorption of Bi VO4 quantum dots and intimate contact with the oxide substrate. This result not only demonstrates a simple method to prepare Bi VO4 quantum dots based solar cells, but also provides important insights into the low bandgap oxide SSSCs.