Precisely Control Relationship between Sulfur Vacancy and H Absorption for Boosting Hydrogen Evolution Reaction

Ef fective and robust catalyst is the core of water splitting to produce hydrogen.Here, we report an anionic etching method to tailor the sulfur vacancy(VS) of NiS_(2) to further enhance the electrocatalytic performance for hydrogen evolution reaction(HER). With the VS concentration change from 2.4% to 8.5%, the H* adsorption strength on S sites changed and NiS_(2)-VS 5.9% shows the most optimized H* adsorption for HER with an ultralow onset potential(68 m V) and has long-term stability for 100 h in 1 M KOH media. In situ attenuated-total-reflection Fourier transform infrared spectroscopy(ATR-FTIRS) measurements are usually used to monitor the adsorption of intermediates. The S-H* peak of the Ni S_(2)-VS 5.9% appears at a very low voltage, which is favorable for the HER in alkaline media. Density functional theory calculations also demonstrate the Ni S_(2)-VS 5.9% has the optimal |ΔG^(H*)| of 0.17 e V. This work offers a simple and promising pathway to enhance catalytic activity via precise vacancies strategy.

Engineering asymmetric electronic structure of cobalt coordination on CoN_(3)S active sites for high performance oxygen reduction reaction

The efficacy of the oxygen reduction reaction(ORR) in fuel cells can be significantly enhanced by optimizing cobalt-based catalysts,which provide a more stable alternative to iron-based catalysts.However,their performance is often impeded by weak adsorption of oxygen species,leading to a 2e^(-)pathway that negatively affects fuel cell discharge efficiency.Here,we engineered a high-density cobalt active center catalyst,coordinated with nitrogen and sulfur atoms on a porous carbon substrate.Both experimental and theoretical analyses highlighted the role of sulfur atoms as electron donors,disrupting the charge symmetry of the original Co active center and promoting enhanced interaction with Co 3d orbitals.This modification improves the adsorption of oxygen and reaction intermediates during ORR,significantly reducing the production of hydrogen peroxide(H_(2)O_(2)).Remarkably,the optimized catalyst demonstrated superior fuel cell performance,with peak power densities of 1.32 W cm^(-2) in oxygen and 0.61 W cm^(-2) in air environments,respectively.A significant decrease in H_(2)O_(2) by-product accumulation was observed during the reaction process,reducing catalyst and membrane damage and consequently improving fuel cell durability.This study emphasizes the critical role of coordination symmetry in Co/N/C catalysts and proposes an effective strategy to enhance fuel cell performance.

Modulating Co-Co bonds average length in Co_(0.85)Se_(1-x)S_(x) to enhance conversion reaction for potassium storage

While alloying transition metal chalcogenides(TMCs)with other chalcogen elements can effectively improve their conductivity and electrochemical properties,the optimal alloying content is still uncertain.In this study,we study the influence of dopant concentration on the chemical bonds in TMC and reveal the associated stepwise conversion reaction mechanism for potassium ion storage.According to density function theory calculations,appropriate S-doping in Co0.85Se(Co_(0.85)Se_(1-x)S_(x))can reduce the average length of Co-Co bonds because of the electronegativity variation,which is thermodynamically favourable to the phase transition reactions.The optimal Se/S ratio(x=0.12)for the conductivity has been obtained from experimental results.When assembled as an anode in potassium-ion batteries(PIBs),the sample with optimized Se/S ratio exhibits extraordinary electrochemical performance.The rate performance(229.2 mA h g^(-1)at 10 A g^(-1))is superior to the state-of-the-art results.When assembled with Prussian blue(PB)as a cathode,the pouch cell exhibits excellent performance,demonstrating its great potential for applications.Moreover,the stepwise K+storage mechanism caused by the coexistence of S and Se is revealed by in-situ X-ray diffraction and ex-situ transmission electron microscopy techniques.Hence,this work not only provides an effective strategy to enhance the electrochemical performance of transition metal chalcogenides but also reveals the underlying mechanism for the construction of advanced electrode materials.

A RAPID FLUORIMETRIC DETERMINATION OF TYROSINE IN SERUM BY THE REACTION WITH CERIUM (Ⅳ)

A fluorimetric method for the determination of tyrosine in serum was proposed. The fluoriscence intensity is a linear function of tyrosine content in the range 0-1. 44ug/ml. The percentage of recovery was satisfactory.

CO_(2)地质封存与利用环境下水泥单矿C_(2)S的腐蚀速率

在CO_(2)地质封存和利用过程中,固井水泥容易与井下的酸性介质CO_(2)发生碳酸化反应,腐蚀固井水泥石造成水泥石力学性能大幅度衰退。针对水泥石单矿C_(2)S在CO_(2)地质封存和利用环境中腐蚀反应速率不清晰的问题,通过SEM、XRD以及TG的测试方法,定量分析C_(2)S腐蚀产物的变化规律。根据腐蚀产物CaCO_(3)的摩尔生成率和非稳态扩散渗透模型拟合得到腐蚀反应产物CaCO_(3)的生成系数α。SEM实验结果表明,腐蚀反应后C_(2)S水泥单矿颗粒的表面均有较大改变,生成了部分腐蚀产物CaCO_(3);XRD结果表明,单矿C_(2)S腐蚀产物CaCO_(3)的晶型主要有方解石和文石;TG测试结果表明,C_(2)S水泥单矿随着腐蚀龄期的增加,腐蚀产物的量均明显增加。拟合结果表明,C_(2)S腐蚀产物生成速率随着温度的升高而增大,90℃下CaCO_(3)腐蚀产物的生成速率系数α最大为54.90。

A review of recent researches on Bunsen reaction for hydrogen production via S–I water and H2S splitting cycles

The Bunsen reaction is the center reaction for both the sulfur–iodine water splitting cycle for hydrogen production and the novel hydrogen sulfide splitting cycle for hydrogen and sulfuric acid production from the sulfur-containing gases.This paper reviews the research progress of the Bunsen reaction in recent 10–15 years.Researches were initially focused on the optimization of the operating conditions of the conventional Bunsen reaction requiring excessive water and iodine to improve the products separation efficiency and to avoid the side reactions and iodine vapor deposition.Alternative methods including electrochemical methods,precipitation methods,and non-aqueous solvent methods had their respective advantages,but still faced challenges.In development of the technology of H2S splitting cycle,dissolving iodine in toluene solvent could render the Bunsen reaction to occur with the flowable I2 stream at ambient temperature such that the side reactions and iodine vaporization can be avoided and the corrosion hazard lessened.It also prevented the Bunsen reaction from using excessive iodine and water.The products from the Bunsen reaction including HI,H2SO4,H2O,and toluene could be directly electrolyzed.

α-Oxoketene Cyclic S, S-cetals Chemistry-Substitution Reaction of α,α'-Dicinnamoyl Ketene Cyclic S, S-Acetals with Ethylenediamine

α,α'-Dicinnamoyl ketene cyclic S, S-acetals 4 were reacted with ethylenediamine to afford α,α'-dicinnamoyl ketene cyclic N,N-acetals 5. This process provides a new method for thesynthesis of 5 in high yield under mild conditions.

Hepatitis C virus in human B lymphocytes transformed by Epstein-Barr virus in vitro by in situ reverse transcriptase-polymerase chain reaction

AIM: To study persistence and replication of hepatitis C virus (HCV) in patients' peripheral blood mononuclear cells (PBMC) cultured in vitro. METHODS: Epstein Barr virus (EBV) was used to transform the hepatitis C virus from a HCV positive patient to permanent lymphoblastoid cell lines (LCL). Positive and negative HCV RNA strands of the cultured cells and growth media were detected by reverse transcriptase-polymerase chain reaction (RT-PCR) each month. Core and NS5 proteins of HCV were further tested using immunohistochemical SP method and in situ RT-PCR. RESULTS: HCV RNA positive strands were consistently detected the cultured cells for one year. The negative-strand RNA in LCL cells and the positive-strand RNA in supernatants were observed intermittently. Immunohistochemical results medicated expression of HCV NS3 and C proteins in LCL cytoplasm mostly. The positive signal of PCR product was dark blue and mainly localized to the LCL cytoplasm. The RT-PCR signal was eliminated by overnight RNase digestion but not DNase digestion. CONCLUSION: HCV may exist and remain functional in a cultured cell line for a long period.

Preparation of Gd_2O_2S:Pr Scintillation Ceramics by Pressureless Reaction Sintering Method

Fabrication of Gd2O2S：Pr scintillation ceramics by 2Gd2O3.（Gd,Pr）2（SO4）3.mH2O precursor was made Gd2O3, Pr6O11 and H2SO4 as the starting materials pressureless reaction sintering was investigated. The by hydrothermal reaction using commercially available Then single phase Gd2O2SO4：Pr powder was obtained by calcining the precursor at 750℃ for 2 h. The Gd2O2SO4：Pr powder compacts can be sintered to single phase Gd2O2S：Pr ceramics with a relative density of 99% and mean grain size of 30um at 1750℃ for 2 h in flowing hydrogen atmosphere. Densification and microstructural development of the Gd2O2S：Pr ceramics were examined. Luminescence spectra of the Gd2O2S：Pr ceramic under 309 nm UV excitation and X-ray excitation show a green emission at 511 nm as the most prominent peak, which corresponds to the ^3p0-3H4 transition of Pr^3＋ ions.

Rapid detection of sepsis complicating acute necrotizing pancreatitis using polymerase chain reaction

INTRODUCTIONAcute narcotizing pancreatitis usually takes a severe clinical course and is associated with multiple organ dysfunction .With the further understanding of pathophysiological events of acute pancreatisis and the therapeutic measuses taken by the clinicians ,the patients can pass through the critical carry stages ,and then the septic complication caused by rtanslocated bacteria, mostly gram-negative microbes from the intestines ensues[1].

Three-dimensional lily-like CoNi_2S_4 as an advanced bifunctional electrocatalyst for hydrogen and oxygen evolution reaction

Designing low-cost, highly efficient, and stable bifunctional electrocatalysts for both hydrogen evolution reaction（HER） and oxygen evolution reaction（OER） is of vital significance for water splitting.Herein, three-dimensional lily-like CoNi_2S_4 supported on nickel foam（CoNi_2S_4/Ni） has been fabricated by sulfuration of the Co–Ni precursor. As expected, CoNi_2S_4/Ni possesses such outstanding electrocatalytic properties that it requires an overpotential of only 54 mV at 10 mA cm^（-2） and 328 mV at 100 mA cm^（-2） for HER and OER, respectively. Furthermore, by utilizing the CoNi_2S_4/Ni electrodes as bifunctional electrocatalysts for overall water splitting, a current density of 10 mA cm^（-2） can be obtained at a voltage of only 1.56 V.

A modified model for isothermal homogeneous and heterogeneous reactions in the boundary-layer flow of a nanofluid

The homogeneous and heterogeneous reactions in the boundary-layer of a flat surface are considered. The autocatalysts are assumed to be of regular sizes, while the solution is a dilute nanofluid. The heat release due to the chemical reactions is taken into account. The Buongiorno’s model is used to describe the behaviors of this reaction system. This configuration makes the current model be different from all previous publications. Multiple solutions are given numerically to the rescaled nonlinear system, whose stability is verified. The results show that the strength coefficients of the homogeneous and heterogeneous reactions are key factors to cause the appearance of the multiple solutions in the distribution of the chemical reactions. Nanofluids enhance the diffusion of heat and help maintain the stability of chemical reactions.

Thermodynamic study on reaction path of Hg(Ⅱ) with S(Ⅱ) in solution

The mercury sulfidation experiments were conducted in the pH range from 1 to 13. The results show that Hg（II） reacted with equimolar S（ II ） has the lowest remained Hg（II ） concentration （9.7 μg/L） at pH 1.0 and the highest remained concentration （940.8μg/L） at pH 13.0. Meanwhile, the changes of pH values were monitored exactly, which reveal that solution pH values change when mixing the same pH value solutions of HgCI2 and Na2S. In order to explain the phenomena and determine the reaction paths of Hg（II） reacting with S（ II ） in the solution, the concerned thermodynamics was studied. Species of S（ II ）-H2O system and Hg（II）-H2O system at different pH values were calculated, and then the species distribution diagrams of S（II）-H2O system, Hg（ II ）-H2O system and Hg（ II ）-Cl-OH--H20 system were drawn. Combining the experimental data and thermodynamic calculation, the mechanism of Hg（II） reacting with S（II） was deduced. The results indicate that different species of S（ II ） and Hg（II） have the diverse reaction paths to form HgS precipitate at different pH values and the standard Gibbs free energies change （△tGm^⊙） of those equations are also calculated, which can provide a guidance for mercury-containing wastewater treatment with Na2S.

Fe,N,S-doped porous carbon as oxygen reduction reaction catalyst in acidic medium with high activity and durability synthesized using CaCl_2 as template

Proton exchange membrane fuel cells suffer from the sluggish kinetics of the oxygen reduction reaction(ORR)and the high cost of Pt catalysts.In the present work,a high‐performance ORR catalystbased on Fe,N,S‐doped porous carbon(FeNS‐PC)was synthesized using melamine formaldehyderesin as C and N precursors,Fe(SCN)3as Fe and S precursors,and CaCl2as a template via a two‐stepheat treatment without a harsh template removal step.The results show that the catalyst treated at900℃(FeNS‐PC‐900)had a high surface area of775m2/g,a high mass activity of10.2A/g in anacidic medium,and excellent durability;the half‐wave potential decreased by only20mV after10000potential cycles.The FeNS‐PC‐900catalyst was used as the cathode in a proton exchangemembrane fuel cell and delivered a peak power density of0.49W/cm2.FeNS‐PC‐900therefore hasgood potential for use in practical applications.

PHOTOINDUCED S_(RN)1 REACTIONS OF ARYL HALIDES WITH CARBAZOLYL NITROGEN ANION

The photoinduced reactions of aryl halides with carbazolyl nitrogen anion,in dimethyl sulfoxide,yield the corresponding N-arylated products.These reactions are suggested in terms of the S;Nl mechaism of nucleophilic substitution.

N/S co-doped 3D carbon framework prepared by a facile morphology-controlled solid-state pyrolysis method for oxygen reduction reaction in both acidic and alkaline media

Developing high-performance non-precious metal electrocatalysts for oxygen reduction reaction(ORR)is crucial for the commercialization of fuel cells and metal-air batteries.However,doped carbon-based materials only show good ORR activity in alkaline medium,and become less effective in acidic environment.We believe that an appropriate combination of both ionic and electronic transport path,and well dopant distribution of doped carbon-based materials would help to realize high ORR performance un-der both acidic and alkaline cond让ions.Accordingly,a nitrogen and sulfur co-doped carbon framework with hierarchical through-hole structure is fabricated by morphology-controlled solid-state pyrolysis of poly(aniline-co-2-ami no thiophenol)foam.The uniform high concentrations of nitrogen and sulfur,high intrinsic conductivity,and integrated three dimensional ionic and electronic transfer passageways of the 3D porous structure lead to synergistic effects in catalyzing ORR.As a result,the limiting current density of the carbonized poly(aniline-co-2-aminothiophenol)foam is equivalent to commercial Pt/C in acidic environment,and twice the latter in alkaline medium.

Bischler-Napieralski Reaction of 2-(3,4-Dimethoxy-2-nitrophenyl)-N-[2-(3,4-dimethoxyphenyl)ethyl]-N-[(S)-1-phenylethyl] acetamide Accompanied by Elimination of Chiral Auxiliary

Unexpected dealkylation of Bischler-Napieralski cyclization of 2-(3,4-dimethoxy-2- nitro-phenyl)-N-[2-(3,4-dimethoxyphenyl) ethyl]-N-[(S)-1-phenyl-ethyl] acetamide 3 was reported. The electronic effect of the substituent at 2-position of C ring was also discussed.

DFT Study on the (S)-Proline-catalyzed Direct Aldol Reaction between Acetone and 4-Nitrobenzaldehyde

DFT/6-31G^＊ calculations were applied to study the direct aldol reaction between acetone and 4-nitrobenzaldehyde catalyzed by （S）-proline. Four transition states associated with the stereo-controlling step, corresponding to syn and anti arrangements of methylene moiety related to the carboxylic acid group in enamine intermediate and re and si attacks to the aldehyde carbonyl carbon have been obtained. The solvent effect of DMSO was investigated with polarized continuum model. The computed energies of transition states reveal the stereo-selectivity of the reaction.

Mechanism analysis of reaction S+(2D)+H2(X1Σg^+) → SH+(X3Σ-) + H(2S) based on the quantum state-to-state dynamics

We present a state-to-state dynamical calculation on the reaction S++ H2→ SH+ +H based on an accurate X2 A″ potential surface. Some reaction properties, such as reaction probability, integral cross sections, product distribution, etc.,are found to be those with characteristics of an indirect reaction. The oscillating structures appearing in reaction probability versus collision energy are considered to be the consequence of the deep potential well in the reaction. The comparison of the present total integral cross sections with the previous quasi-classical trajectory results shows that the quantum effect is more important at low collision energies. In addition, the quantum number inversion in the rotational distribution of the product is regarded as the result of the heavy–light–light mass combination, which is not effective for the vibrational excitation. For the collision energies considered, the product differential cross sections of the title reaction are mainly concentrated in the forward and backward regions, which suggests that there is a long-life intermediate complex in the reaction process.

CRYSTAL STRUCTURE OF (Et_4N)_2Pd(i-MNT)_2AND ITS REACTION WITH (Et_4N)_2WS_4(i-MNT=S_2CC(CN)_2￣2-)

Et4N)2pd(i-mnt)2.fw = 647. 04, monoclinic,space group P21/c;a =9.511(1), b = 11.612(2), c=14.820(3)A,g= 94.38(1)',I'= 1631.9(5)A;7=2' D.=1.32g.cnl-;F (000)=672, R=0 0324, R. = 0'0298.Tills is a new e,\alil[)le ot' X-raycharacterized Pd colllplexes with bivalent anion l,1 -dithiolato ligands an(i IIis reactioll witll(Et'N)zWS# gives (Et4N)ZWS4Pd(i-1lint).