2,5-Diformylfuran production by photocatalytic selective oxidation of 5-hydroxymethylfurfural in water using MoS_(2)/CdIn_(2)S_(4) flower-like heterojunctions

The selective oxidation of 5-hydroxymethylfurfural(HMF) into 2,5-diformylfuran(DFF) is an important reaction for renewable biomass building blocks. Compared with thermal catalytic processes, photocatalytic production of DFF from HMF has attracted tremendous attention. Herein, the MoS_(2)/CdIn_(2)S_(4)(MC)flower-like heterojunctions were prepared and considered as photocatalysts for selective oxidation of HMF into DFF under visible-light irradiation in aqueous solution. Results demonstrated MoS_(2) in MC heterojunction could promote the separation of photoexcited electron-hole pairs, while the amount of MoS_(2) dropping was proved influenced on the photocatalytic performance. 80.93% of DFF selectivity was realized when using 12.5% MC as photocatalyst. In addition, the MC catalyst also showed great potential in transformation of other biomass derived benzyl-and furyl-alcohols. The catalytic mechanism suggested that ·O_(2)^(-) was the decisive active radical for HMF oxidation. Therefore, the MC heterojunction could be applied in photocatalytic conversion of biomass to valuable chemicals under ambient condition.

Pressure-Dependent Point-Contact Spectroscopy of Superconducting PbTaSe2 Single Crystals

We develop an experimental tool to investigate the order parameter of superconductors by combining pointcontact spectroscopy measurement with high-pressure technique.It is demonstrated for the first time that planar point-contact spectroscopy measurement on noncentrosymmetric superconducting PbTaSe2 single crystals is systematically subjected to hydrostatic pressures up to 12.1 kbar.Under such a high pressure,the normal-state contact resistance is sensitive to the applied pressure,reflecting the underlying variation of contact transparency upon pressures.In a superconducting state,the pressure dependence of the energy gap△0 and the critical temperature Tc for gap opening/closing are extracted based on a generalized Blond-Tinkham-Klapwijk model.The gap ratio 2△0/kB Tc indicates a crossover from weak coupling to strong coupling in electron pairing strength upon pressure for PbTaSe2.Our experimental results show the accessibility and validity of high-pressure pointcontact spectroscopy,offering rich information about high-pressure superconductivity.

Ultrathin polyamide nanofiltration membrane prepared by triazine-based porous organic polymer as interlayer for dye removal

Separation membrane with high flux is generally encouraged in industrial application,because of the tremendous needs for decreasing membrane areas,usage costs and space requirements.The most effective and direct method for obtaining the high flux is to decrease membrane thickness.Polyamide(PA)nanofiltration membrane is conventionally prepared by the direct interfacial polymerization(IP)on substrate surface,and results in a thick PA layer.In this work,we proposed a strategy that constructing triazine-based porous organic polymer(TRZ-POP)as the interlayer to prepare the ultrathin PA nanofiltration membranes.TRZ-POP is firstly deposited on the polyethersulfone substrate,and then the formed TRZ-POP provides more adhesion sites towards PA based on its high specific surface areas.The chemical bonding between terminal amine group of TRZ-POP and the amide group of PA further improves the binding force,and strengthens the stability of PA layer.More importantly,the high porosity of TRZPOP layer causes the higher polymerization of initial PA owning to the stored sufficient amino monomer;and H-bonding interaction between amine groups of TRZ-POP and piperazine(PIP)can astrict the release of PIP.Thus,IP process is controlled,and the thinnest thickness of prepared PA layer is only<15 nm.As expected,PA/TRZ-POP membrane shows a more excellent water flux of 1414 L·m^(-2)·h^(-1)·MPa^(-1)than that of the state-of-the-art nanofiltration membranes,and without sacrificing dye rejection.The build of TRZPOP interlayer develops a new method for obtaining a high-flux nanofiltration membrane.

H_(3)PO_(4) activated biochars derived from different agricultural biomasses for the removal of ciprofloxacin from aqueous solution

Biochars were prepared by the pyrolysis of various H_(3)PO_(4) activated agricultural biomasses at 600℃and subsequently used as adsorbents for the removal of ciprofloxacin(CIP)from aqueous solution.Peanut shell-based biochar(PSBC),corncob-based biochar(CCBC)and cotton-based biochar(CTBC)had high surface areas(571.0-1006.3 m^(2)/g),well-developed pore structures(mesopores with large pore volumes)and available adsorption functional groups(C=C,C-N and C-O-C).The CIP adsorption onto the biochars was investigated by batch experiments(kinetics,isotherms,thermodynamics,pH,etc.).Thermodynamics calculations showed the spontaneous(ΔG^(θ)<0)and endothermic(ΔH^(θ)>0)nature of the mechanism.In particular,CCBC exhibited high adsorption capacity(120.6 mg/g)of CIP in real lake water and it also had significant removal efficiency of other common pharmaceutical contaminants from real lake environ-ment,and even in a coexisting quintuple system.Finally,multiple interaction mechanisms of CIP adsorption onto aromatized biochar were explored combining characterization analysis and theoretical calculations.Elucidation of the mechanism of CIP adsorption onto biochar provides new insights into the assessment of the removal of pharmaceuticals from the aqueous environment.

Tunneling Barrier Thickness Dependence of Spin Polarization of Ferromagnet in Magnetic Tunnel Junctions

For designing low-impedance magnetic tunnel junctions(MTJs),it has been found that tunneling magnetoresistance strongly correlates with the insulating barrier thickness,imposing a fundamental problem about the relationship between spin polarization of ferromagnet and the insulating barrier thickness in MTJs.Here,we investigate the influence of alumina barrier thickness on tunneling spin polarization(TSP)through a combination of theoretical calculations and experimental verification.Our simulating results reveal a significant impact of barrier thickness on TSP,exhibiting an oscillating decay of TSP with the barrier layer thinning.Experimental verification is realized on FeNi/AlO_(x)/Al superconducting tunnel junctions to directly probe the spin polarization of FeNi ferromagnet using Zeeman-split tunneling spectroscopy technique.These findings provide valuable insights for designs of high-performance spintronic devices,particularly in applications such as magnetic random access memories,where precise control over the insulating barrier layer is crucial.

基于窖泥微生物相对定量与绝对定量联用的窖泥老熟特征分析

【目的】基于传统的相对定量法,在总DNA提取过程中加入内标菌,探索不同老熟程度下窖泥微生物菌群组成特征。【方法】通过添加外源菌丙酮丁醇梭菌(Clostridium acetobutylicum)作为内标菌,利用16S rRNA基因扩增子测序技术,基于相对丰度与绝对丰度解析不同老熟程度窖泥内的菌群结构和理化差异。【结果】相对定量分析表明,随着窖泥老熟,窖泥微生物群落的多样性增加,己酸菌属(Caproiciproducens)、甲烷杆菌属(Methanobacterium)、甲烷八叠球菌属(Methanosarcina)和互营单胞菌属(Syntrophomonas)等菌的相对丰度显著增高。结合绝对丰度分析,老熟窖泥内的生物量分别是新窖泥与趋老熟窖泥的600倍与28倍。不同于相对定量分析,乳杆菌属(Lactobacillus)的绝对丰度在老熟窖泥内并未降低,为新窖泥的20倍。己酸菌属在老窖泥中的绝对丰度为新窖泥的25000倍;其他功能微生物包括甲烷杆菌属、甲烷八叠球菌属、甲烷短杆菌属(Methanobrevibacter)、互营单胞菌属的绝对丰度也随着窖龄的增加而显著增加。菌群结构的绝对定量动态分析表明,新窖泥转变为老熟窖泥的过程是一个菌群组成多样性不断提高、生物量也逐步增加的过程,老窖泥中己酸菌属、互营单胞菌属、多种甲烷菌等微生物绝对量的增加,推测对降低窖泥内的乳酸含量和形成窖泥稳态环境具有重要作用。【结论】绝对定量方法的引入,可观测不同窖龄窖泥微生物生物量的差异,解析不同老熟阶段窖泥功能微生物绝对丰度的动态变化,为窖泥菌群结构和代谢功能的定量化和因果关系研究提供了新的策略。

克氏梭菌硫解酶的鉴定及其功能研究

【目的】硫解酶是梭菌属微生物合成短中链脂肪酸的关键酶。克氏梭菌(Clostridium kluyveri)具有3个高度同源的硫解酶编码基因,对这3个基因的功能鉴定是解析克氏梭菌高己酸合成能力的关键。【方法】通过发酵动力学分析确定克氏梭菌的己酸和丁酸生成动力学特征;转录组测序结合反转录-荧光定量RCR分析克氏梭菌3个硫解酶编码基因的表达水平和时序表达特征;在大肠杆菌中异源表达这3个硫解酶,并对其硫解酶动力学参数进行测定。【结果】克氏梭菌生成丁酸、己酸、辛酸,其中己酸为主要代谢产物;转录组数据显示,在乙酸消耗完全之前,thlA1基因维持恒定表达,thlA2基因表达时序上调,thlA3基因表达时序下调,转录组测序表明3个硫解酶编码基因均具有较高水平的转录活性,thlA2和thlA3的最高表达量分别约为thlA1的29%和43%;硫解酶动力学参数测定结果表明,克氏梭菌3个硫解酶对于四碳底物均显示出相似的底物亲和力(K_m),但ThlA1对四碳底物的催化效率(k_(cat)/K_m)略低于ThlA2和ThlA3。【结论】克氏梭菌的3个硫解酶均具有催化活性,在克氏梭菌体内均呈活跃表达,表明克氏梭菌拥有3个具有催化活性的硫解酶,这为后续深入研究克氏梭菌己酸合成机理奠定了基础。

Promoting catalysis activity with optimizable self-generated Co-Fe alloy nanoparticles for efficient CO_(2)electrolysis performance upgrade

Stable and flexible metal nanoparticles(NPs)with regeneration ability are critical for long-term operation of solid oxide electrolysis cells(SOECs).Herein,a novel perovskite electrode with stoichiometric Pr_(0.4)Sr_(0.6)Co_(0.125)Fe_(0.75)Mo_(0.125)O_(3)−δ(PSFCM)is synthesized and studied,which undergoes multiple redox cycles to validate its structural stability and NPs reversibility.The Co-Fe alloy has exsolved from the parent bulk under reducing atmosphere,and is capable of reincorporation into the parent oxide after re-oxidation treatment.During the redox process,we successfully manipulate the size and population density of the exsolved NPs,and find that the average particle size significantly reduces but the population density increases correspondingly.The electrode polarization resistance of the symmetric cell remains stable for 450 h,and even activates after the redox cycling,which may be attributed to the higher quantity and larger specific surface area of the regenerated Co-Fe alloy NPs.Moreover,the electrochemical performance towards carbon dioxide reduction reaction(CO_(2)RR)is evaluated,and the CO_(2)electrolyzer consisting of CoFe@PSCFM-Ce_(0.8)Sm_(0.2)O_(1.9)(SDC)dual-phase electrode exhibits an excellent current density of 1.42 A·cm^(−2)at 1.6 V,which reaches 1.7 times higher than 0.83 A·cm^(−2)for the pristine PSCFM electrode.Overall,with this flexible and reversible high-performance SOEC cathode material,new options and perspectives are provided for the efficient and durable CO_(2)electrolysis.