温度对丙酮酸生物合成动力学、能荷和氧化-还原度的影响

在光滑球拟酵母(Torulopsis glabrata620)生产丙酮酸的过程中,温度对丙酮酸生物合成有着重要的影响。考察了不同发酵温度下基质消耗、细胞生长、丙酮酸合成及能荷水平和氧化-还原度等方面的差异。在恒温发酵中,维持较高的发酵温度可以增强糖耗,促进菌体生长,加速丙酮酸积累,但前期胞内能荷水平较高,菌体消耗较多葡萄糖合成菌体,后续产酸能力不足,导致丙酮酸得率降低;维持较低的发酵温度可以在发酵后期提供稳定的产酸能力,但菌体代谢缓慢,后期胞内NADH/NAD+水平较高,丙酮酸生产强度降低。因此仅仅采取单一的温度控制策略很难达到丙酮酸高产量、高产率和高生产强度的统一。

Insights into Reduction of CO_(2)to CO Catalyzed by Pyramidal-4Ni Clusters Supported on Doped CeO_(2)

Converting CO_(2)into valuable chemicals has become a widely used research method for CO_(2)conversion.In this work,the catalytic performance of pyramidal-4Ni catalysts supported on rare earth metal-doped CeO_(2)towardCO_(2)reductionreaction(CO_(2)RR)was investigated by using density-functional theorycalculations.For rare earth metal-doped CeO_(2),2Ce is substituted by 2 trivalent cations and at the same time one oxygen vacancy is created to make charge compensation.We investigated the oxygen vacancy nearest(Vo,N)and next-nearest(Vo,NN)to 4Ni,and found releasing CO and CO_(2)dissociation are the rate-determining steps,respectively,via the path of Vo,N and Vo,NN.Among the studied dopants(Ga,Sb,Lu,Gd,Pr,La,Bi),Gd is identified as the best dopant for catalyzing the reduction of CO_(2)at 823 K,with the turn-over frequency(TOF)of 104 times as large as that over 4Ni supported on pure CeO_(2).This exploration provides theoretical support and guidance for the research and application of rare earth metaldoped CeO_(2)-loaded Ni catalysts in the field of CO_(2)reduction.

Effect of calcination temperatures on photocatalytic H_(2)O_(2)-production activity of ZnO nanorods

Photocatalytic hydrogen peroxide(H_(2)O_(2))production from O_(2) and H2O is an ideal process for solar‐to‐chemical energy conversion.Herein,ZnO nanorods are prepared via a simple hydrothermal method for photocatalytic H_(2)O_(2) production.The ZnO nanorods exhibit varied performance with different calcination temperatures.Benefiting from calcination,the separation efficiency of photo‐induced carriers is significantly improved,leading to the superior photocatalytic activity for H_(2)O_(2) production.The H_(2)O_(2) produced by ZnO calcined at 300℃ is 285μmol L^(−1),which is over 5 times larger than that produced by untreated ZnO.This work provides an insight into photocatalytic H2O2 production mechanism by ZnO nanorods,and presents a promising strategy to H2O2 production.

Activation of small molecules over praseodymium-doped ceria

Praseodymium can modify the properties of ceria (CeO2), changing the electronic structure, reducibility and catalytic behavior. Oxygen vacancies in the ceria-based samples can activate C–O and C–H bonds of small molecules such as CO2 and propane. Partially reduced Pr/CeO2-x can selectively activate C–H of propane, giving a propylene selectivity of ca. 75% at a propane conversion of 5% to 10%. Excess reduction of Pr/CeO2-x induces coking reactions during propane dehydrogenation, resulting in fast catalyst deactivation.

La-doped TiO_(2) nanorods toward boosted electrocatalytic N_(2)-to-NH_(3)conversion at ambient conditions

Electrochemical N_(2) reduction provides a green and sustainable alternative to the Haber-Bosch technology for NH_(3 )synthesis.However,the extreme inertness of N_(2) molecules is a formidable challenge,which requires the development of an active electrocatalyst to drive the N_(2) reduction reaction(NRR)for NH_(3) production at ambient conditions.Herein,we demonstrate the development of La-doped TiO_(2) nanorods as an efficient NRR electrocatalyst for ambient NH3 synthesis.The optimized La-TiO_(2) catalyst offers a large NH_(3) yield of 23.06 pg h1 mgcat 1 and a high Faradaic efficiency of 14.54%at-0.70 V versus reversible hydrogen electrode in 0.1 M L1CIO_(4),outperforming most La-and Ti-based catalysts reported before.Significantly,it also demonstrates high electrochemical stability and its activity decay is negligible after 48 h test.The mechanism is further revealed by density functional theory calculations.

Enhanced oxygen reduction reaction performance over Pd catalysts by oxygen-surface-modified SiC

Obtaining a detailed understanding of the surface modification of supports is crucial;however,it is a challenging task for the development and large-scale fabrication of supported electrocatalysts that can be used as alternatives to Pt-based catalysts for the oxygen reduction reaction(ORR).In this study,commercial silicon carbide(SiC)was modified through surface oxidization(O-SiC)to support the use of Pd nanoparticles(Pd NPs)as electrocatalysts for ORR.The obtained Pd/O-SiC catalysts exhibited better ORR activity,stronger durability,and higher resistance to methanol poisoning than that exhibited by commercial Pt/C.The role of the support in enhancing the ORR performance,especially the oxidization of SiC surfaces,was discussed in detail based on the experimental characterizations and density functional theory calculations.The underlying mechanism of the superior ORR performance of Pd/O-SiC catalysts was attributed to the charge transfer from SiC_(x)O_(y)to Pd NPs on the surfaces of SiC and the strong metal–support interactions(SMSIs)between Pd and SiC_(x)O_(y).The charge transfer enhanced the ORR activity by inducing electron-rich Pd,increased the adsorption of the key intermediate OOH,and decreased the Gibbs free energy of the critical ORR step.Furthermore,SMSIs enhanced the ORR stability of the Pd/O-SiC catalyst.This study provided a facile route for designing and developing highly active Pd-based ORR electrocatalysts.

Supercritical synthesis of platinum-modified titanium dioxide for solar fuel production from carbon dioxide

This paper investigates the properties of TiO2‐based photocatalysts synthesised under supercriticalconditions.Specifically,the characteristics of Pt dispersed on TiO2catalysts obtained in supercriticalCO2are discussed and compared with those of commercial TiO2.The photocatalytic activity of thesynthesised catalysts in the CO2photoreduction reaction to produce solar fuel is tested.The mainconclusion of the study is that photocatalysts with better or similar features,including high surfacearea,crystallisation degree,hydroxyl surface concentration,pore volume,absorbance in the visiblerange and methane production rate,to those of commercial TiO2may be produced for the reductionof CO2to fuel by synthesis in supercritical media.

Bioleaching of chalcopyrite with Acidianus manzaensis YN25 under contact and non-contact conditions

In order to investigate the contributions of contact and non-contact cells of Acidianus manzaensis(A.manzaensis) YN25 to the bioleaching of chalcopyrite,three experiments were carried out in the modified shake flasks.The redox potential,pH,cell density,copper and iron ions in the solution were monitored,and the morphological feature and chemical composition of the leached residues were analyzed.The highest leaching efficiency of Cu and Fe was reached in the experiment where the A.manzaensis YN25 could contact the surface of the chalcopyrite.There was no precipitation of jarosite in the leached residues of three experiments,but there was elemental sulfur in the leached residues when the cells could not contact the chalcopyrite.From these results,it is apparent that the leaching of the chalcopyrite is the cooperative action of the contact and non-contact A.manzaensis YN25.

Solvation structure and dynamics of Li and LiO_(2)and their transformation in non-aqueous organic electrolyte solvents from first-principles simulations

Density functional theory calculations together with ab initio molecular dynamics(AIMD)simulations have been used to study the solvation,diffusion and transformation of Li^(+)and LiO_(2)upon O_(2)reduction in three organic electrolytes.These processes are critical for the performance of Li-air batteries.Apart from studying the structure of the solvation shells in detail,AIMD simulations have been used to derive the diffusivity and together with the Blue Moon ensemble approach to explore LiO_(2)formation from Li^(+)and O_(2)−and the subsequent disproportionation of 2LiO_(2)into Li_(2)O_(2)+O_(2).By comparing the results of the simulations to gas phase calculations,the impact of electrolytes on these reactions is assessed which turns out to be more pronounced for the ionic species involved in these reactions.

String and Ball-Like TiO_2/rGO Composites with High Photo-catalysis Degradation Capability for Methylene Blue

Novelthree-dimensionalstring and ball-like titanium dioxide/reduced graphene oxide, TiO_2/rGO(STG) composites were prepared using a one-step hydrolysis process followed by a low-temperature hydrothermaltreatment. The STG composites exhibited excellent photo-catalytic degradation performance for methylene blue owing to a good synergistic effect between TiO_2 and rGO. The STG composites with 1.0 wt% of rGO loading exhibited the highest removalrate of 86.0% for methylene blue and its reaction rate constant(5.27 × 10^(-3) min^(-1)) was much higher than those of pure string and ball-like TiO_2(ST). In addition, the STG composites also showed an outstanding capability for the photo-catalysis degradation of other cationic dyes. In addition, a possible photo-catalytic degradation mechanism for the STG composite was postulated, in which~?O_2^- and~·OH were the main oxidizing groups. This work of fers new insights into a better design and preparation of novelcomposite materials for the removalof organic dyes.

Reduction smelting on bismuth oxide residue in FeO-SiO2-CaO ternary slag system

Reduction smelting of the bismuth oxide residue from pressure leaching of bismuth sulfide was investigated in the FeO-SiO_2-CaO ternary slag system.The results show that all the recovery ratios of Bi,Ag,Cu and Pb increase with the increase of reductive coal proportion,reaction temperature and time,while too much reductive coal would help Fe enter metal phase;CaO/SiO_2and Fe O/SiO_2 of the chosen slag system should be 0.5-0.75 and 1.25-1.75,respectively,for the reason that the slag system has the optimum mobility and is beneficial for the recovery of metals.The corresponding optimum conditions are determined as follows:the added coal proportion is 7%of the leaching residue,CaO/SiO_2 mass ratio in the chosen slag system is 0.5 and FeO-SiO_2 is 1.5,the reaction temperature is 1300°C and the reaction time is 40 min.Under the above conditions,the recovery ratios of Bi,Ag,Cu and Pb are 99.6%,99.8%,97.0%and 97.3%,respectively.

Reduction of lead sulfate to lead sulfide with carbon monoxide

In order to decrease the solubility of PbSO4 and enhance lead recovery from PbSO4 bearing wastes, CO was employed as a reductant to transform PbSO4 into Pb S. Reaction system was established and reductive thermodynamics of PbSO4 was calculated by software HSC 5.0. The effects of gas concentration, reaction temperature, time and mass of sample on reduction of PbSO4 were examined by thermogravimetry(TG) and XRD. Roasting tests further verify the conclusions of thermodynamic and TG analyses. The results show that increasing temperature in the reasonable range and CO content are favorable for the formation of Pb S. The reduction process is controlled by chemical reaction and calculation value of the activation energy is 47.88 k J/mol.

Sticking of iron ore pellets in direct reduction with hydrogen and carbon monoxide:Behavior and prevention

A series of reduction experiments of iron ore pellets with hydrogen,carbon monoxide and their mixture were carried out in a laboratory scale shaft furnace.The sticking behavior accompanying reduction of iron ore pellets was investigated.And morphology of the sticking interface forming during reduction was analyzed by SEM equipped with EDS.In order to evaluate the effects of the temperature and gas composition on sticking properties,reduction of iron ore pellets were conducted at 800-1000 ℃.The results show that the sticking strength of the pellets increases with temperature,however,decreases with hydrogen content in reducing gas.For an efficient shaft furnace operation in direct reduction(DR),relative prevention of sticking such as coating of pellets was also developed to solve sticking problem.The results show that CaO is a suitable material for the coating method.

Catalytic activity of V_(2)CO_(2) MXene supported transition metal single atoms for oxygen reduction and hydrogen oxidation reactions:A density functional theory calculation study

Two-dimensional(2D)MXene and single-atom(SA)catalysts are two frontier research fields in catalysis.2D materials with unique geometric and electronic structures can modulate the catalytic performance of supported SAs,which,in turn,affect the intrinsic activity of 2D materials.Density functional theory calculations were used to systematically explore the potential of O-terminated V2C MXene(V_(2)CO_(2))-supported transition metal(TM)SAs,including a series of 3d,4d,and 5d metals,as oxygen reduction reaction(ORR)and hydrogen oxidation reaction(HOR)catalysts.The combination of TM SAs and V_(2)CO_(2)changes their electronic structure and enriches the active sites,and consequently regulates the intermediate adsorption energy and catalytic activity for ORR and HOR.Among the investigated TM-V_(2)CO_(2)models,Sc-,Mn-,Rh-,and PtMCCh showed high ORR activity,while Sc-,Ti-,V-,Cr-,and Mn-V_(2)CO_(2)exhibited high HOR activity.Specifically,Mn-and Sc-V_(2)CO_(2)are expected to serve as highly efficient and cost-effective bifunctional catalysts for fuel cells because of their high catalytic activity and stability.This work provides theoretical guidance for the rational design of efficient ORR and HOR bifunctional catalysts.

Carbothermic reduction of alumina with carbon in vacuum

Carbothermic reduction alumina in vacuum was conducted, and the products were analysed by means of XRD and gas chromatography. Thermodynamic analysis shows that in vacuum the initial carbothermic reduction reaction temperature reduces compared with that under normal pressure, and the preferential order of products is Al404C, Al4C3, Al2OC, Al20 and A1. Experiment results show that the carbothermic reduction products of alumina are A1404C and A14C3, and neither A12OC, Al20 or Al was found. During the carbothermic reduction process, the reaction rate of Al203 and carbon decreases gradually with increasing time. Meanwhile, lower system pressure or higher temperature is beneficial to the carbothermic reduction of alumina process. A1404C is firstly formed in the carbothermic reaction, and then A14C3 is formed in lower system pressure or at higher temperature.

Ozonation of Sulfur Dioxide in Sulphuric Acid Solution

In this study, the oxidation rates of sulfur dioxide （SO2） in sulphuric acid solution by ozone and oxygen were compared, and the oxidation mechanism of ozone on SO2 was investigated. The results showed that the oxidation-reduction potential of the acidic solution was enhanced, the transformation rate of sulfuric acid to sulphuric acid was increased and the absorption driving force was improved in the presence of ozone. By comparing the amount of sulfate ions measured in the experiments and the theoretical amount of sulfate ions calculated from the amount of ozone consumed in the reaction, it can be confirmed that oxygen free radicals from dissociation of ozone are reactive as an efficient oxidant and oxygen from ozone generator participates in the reaction with SO2. 0.602 mol of effective oxygen was introduced into the reaction by one mole of ozone in 10.15 rain at sulphuric acid concentration of 3% （by mass）, SO2 concentration of 1.33% （by volume） and oxygen flow rate of 1.5 L.min^-1 from ozone generator.

Dehydrogenase Activity of Soil Microorganisms and the Total DNA Level in Soil of Different Use

The aim of the study was to find the interrelations between the activity of intracellular dehydrogenases, abundance of microorganisms, and the level of soil DNA in the Mollic Gleysol profile, with notification on the dominant DNA form （extra-or intra-cellular）, depending on the type of land use. Two neighbouring meadows were selected for investigations： one systematically cultivated and fertilized and the other deprived of any effect of anthropogenic activity, used as a control. We have demonstrated that dehydrogenase activity （DHA）, the DNA content and microbial abundance strongly depended on the type of land use. DHA exhibited a significant correlation with the DNA content （r = 0.99^＊＊＊ and r = 0.74^＊, for cultivated and control sites, respectively）. This relationship with such a high r value might suggest domination of the intracellular form of DNA in the cultivated meadow, which is also confirmed by the c.a. 13% increase in microorganism abundance in the cultivated soil. The optimal conditions for microbial activities were defined by the significant positive interrelationships between microbial abundance and the total organic carbon content, and a negative correlation with pH, redox potential and soil bulk density.

Electrochemical Energy Storage Technologies and Applications

The current need to fasten the implementation of renewable energies greatly depends on the development of competitive storage devices, and while there is not a single technology which is likely capable to competitively cover the wide range of possible demands, electrochemical technologies are one of the most promising for many of them. For the realization of this promise, new materials fulfilling criteria such as high energy density, high power density, competitive cost, reliability, and environmental compatibility need to be developed in the near future. Electrochemical energy storage devices can be classified into two main technologies： supercapacitors and batteries （including redox flow batteries）. Materials and applications for these technologies are discussed and compared, listing current status, technical and strategic challenges.

Atomic-level-designed copper atoms on hierarchically porous gold architectures for high-efficiency electrochemical CO reduction

Electrochemical CO_(2) reduction is a promising technology for solving the CO_(2) emission problems and producing value-added products. Here, we report a hierarchically porous Cu1Au single-atom alloy(SAA) as an efficient electrocatalyst for CO_(2) reduction. Benefiting from the hierarchically porous architectures with abundant vacancies as well as three-dimensional accessible active sites, the as-prepared nanoporous Cu1Au SAA catalyst shows remarkable CO_(2) reduction performance with nearly 100% CO Faraday efficiency in a wide potential range(-0.4 to -0.9 V vs. reversible hydrogen electrode. The in-situ X-ray absorption spectroscopy studies and density functional theory calculations reveal that the Cu-Au interface sites serve as the intrinsic active centers,which can facilitate the activated adsorption of CO_(2) and stabilize the *COOH intermediate.

In-situ electropolymerized bipolar organic cathode for stable and high-rate lithium-ion batteries

To address the dissolution issue and enhance the electrochemical performance of organic electrode materials,herein, a bipolar organic cathode was prepared by in-situ electropolymerization of amino-phenyl carbazole naphthalene diimide(APCNDI). APCNDI is composed of n-type 1,4,5,8-naphthalene tetracarboxylic diimide that stores Li cations and p-type carbazole groups which react with anions and serve as polymerization sites. Electropolymerization completely eliminated the dissolution problem of APCNDI, and the electropolymerized cathode demonstrated a bipolar reaction with excellent electrochemical performance, stable cycling performance with a capacity retention of 92 mA h g;after1000 cycles, and a superior rate performance of 72 mA h g;at 10 A g;. The bipolar feature and reactions of APCNDI were systematically investigated and verified by multiple characterization techniques. Our findings provide a novel strategy for the design and fabrication of electrodes for high-performance organic batteries.