高效氧催化反应中的金属有机骨架材料（英文）

氧电催化反应包括氧气还原反应(ORR)和氧气析出反应(OER).作为核心电极反应,这两个反应对诸多能源存储与转换技术(比如燃料电池、金属空气电池以及全水分解制氢等)的能量效率起决定性作用.然而,ORR和OER涉及多个反应步骤、多个电子转移过程以及多相界面传质过程.这些复杂的过程较大程度上限制了ORR和OER的反应速率.从理论和实践两个方面来看,ORR和OER都需要高效电催化剂的参与来促进其反应速率,从而能够最终提高上述能源存储与转换技术的能量转换或利用效率.目前,以Pt,Pd,Ir,Ru为代表的贵金属基电催化剂具有十分突出的电催化性能.但是,过高的成本和过低的储量始终制约着贵金属基电催化剂在催化ORR和OER反应方面,乃至在能源存储与转换技术领域的规模化应用.因而,开发高效非贵金属基氧电催化剂成为近年来能源存储与转换领域的研究重点之一.在众多已经报道的非贵金属基氧电催化剂中,金属有机骨架材料(MOFs)备受瞩目.MOFs是一类由有机配体和金属节点通过配位键自组装而成的晶态多孔材料.它们具备超高比表面积、超高孔隙率以及规则性纳米孔道.相比较其他传统的多孔材料(比如活性炭、分子筛、介孔炭、介孔氧化硅等),MOFs最主要的优势在于它们的结构和功能可以依据需求通过选择合适的有机配体和金属节点进行便利地设计,或通过后处理进行必要的改性和调节.基于独特的多孔特性以及结构与功能的可设计、可调节性,MOFs在气体分离与存储、异相催化、化学传感、药物输送、环境保护以及能源存储与转化等领域都具有潜在的应用价值.因而,近年来,MOFs备受基础研究领域和工业界的青睐.针对MOFs开展的基础研究和应用开发逐渐成为诸多领域的研究焦点.也正由于MOFs具有的上述优异特性,尤其是结构与功能的可设计、可调节性,使得设计制备基于单纯MOFs以及MOFs衍生材料成为开发高效非贵金属基氧电催化剂的新途径.本综述首先论述了基于单纯MOFs的氧电催化剂(包括纯MOFs、活性物种修饰的MOFs以及与导电材料构成的复合MOFs)的合成以及它们在ORR或OER催化反应中应用的研究进展.在第二部分论述中,本综述主要针对MOFs衍生的各类氧电催化剂(包括无机微米-纳米结构/多孔碳复合材料、纯多孔碳材料、纯无机微米-纳米结构材料以及单原子型电催化材料)的研究进展进行了简要介绍和讨论.最后,本综述对MOFs基氧电催化剂目前存在的挑战进行了简要分析;同时,也对这类氧电催化剂的通用设计准则以及未来发展方向进行了展望.尽管存在诸多挑战,MOFs始终被认为是极好的'平台'材料.充分利用它们将有利于开发高效且实用的非贵金属基氧电催化剂.

Physiological Response of Mung Bean to Polyethylene Glycol Drought Stress at Flowering Period

The study was carried out on the basis of the flowering period of mung bean (Phaseolus radiatus). The polyethylene glycol 6000 (PEG6000) was used to stimulate water stress. Four mung bean varieties with different drought resistances were used as materials in this experiment, in which the physiological indexes of mung bean for the identification of drought resistance were selected, and the response analysis of seven physiological indexes to different degrees of drought stress was measured by using polyethylene glycol 6000 (PEG6000) on different concentrations of 5%, 10% and 20%. The physiological mechanism was analysed on drought tolerance of mung beans. This test was to set up identification system for drought tolerance of flowering mung bean. The results showed that the relative conductivity after 6 days of 5% PEG treatment, the SOD activity after 6 days of 5% PEG treatment, the POD activity after 6 days of 10% PEG treatment and the ABA content after 6 days of 10% PEG treatment could be used as drought-tolerant identification for mung beans at flowering period. These four physiological indexes and drought-resistant index weighted grey correlation analysis results showed that the correlation order was successively SOD activity (0.8589) > ABA content (0.8290) > conductivity (0.7160) > POD activity (0.6637);and the grey correlation degree was greater than 0.6500 among the four physiological indexes.

Ca^(2+)-dependent TaCCD1 cooperates with TaSAUR215 to enhance plasma membrane H^(+)-ATPase activity and alkali stress tolerance by inhibiting PP2C-mediated dephosphorylation of TaHA2 in wheat

Alkali stress is a major constraint for crop production in many regions of saline-alkali land.However,little is known about the mechanisms through which wheat responds to alkali stress.In this study,we identified a calcium ion-binding protein from wheat,TaCCD1,which is critical for regulating the plasma membrane(PM)H^(+)-ATPase-mediated alkali stress response.PM H+-ATPase activity is closely related to alkali tolerance in the wheat variety Shanrong 4(SR4).We found that two D-clade type 2C protein phosphatases,TaPP2C.D1 and TaPP2C.D8(TaPP2C.D1/8),negatively modulate alkali stress tolerance by dephosphorylating the penultimate threonine residue(Thr926)of TaHA2 and thereby inhibiting PM H+-ATPase activity.Alkali stress induces the expression of TaCCD1 in SR4,and TaCCD1 interacts with TaSAUR215,an early auxin-responsive protein.These responses are both dependent on calcium signaling triggered by alkali stress.TaCCD1 enhances the inhibitory effect of TaSAUR215 on TaPP2C.D1/8 activity,thereby promoting the activity of the PM H^(+)-ATPase TaHA2 and alkali stress tolerance in wheat.Functional and genetic analyses verified the effects of these genes in response to alkali stress,indicating that TaPP2C.D1/8 function downstream of TaSAUR215 and TaCCD1.Collectively,this study uncovers a new signaling pathway that regulates wheat responses to alkali stress,in which Ca^(2+)-dependent TaCCD1 cooperates with TaSAUR215 to enhance PM H+-ATPase activity and alkali stress tolerance by inhibiting TaPP2C.D1/8-mediated dephosphorylation of PM H+-ATPase TaHA2 in wheat.

Single-atom Co-N_(4)catalytic sites anchored on N-doped ordered mesoporous carbon for excellent Zn-air batteries

Developing efficient transition metal-nitrogen-carbon(TM-N-C)catalysts with abundant accessible active sites has been in the limelight in recent years due to their exceptional application potential in Zn-air bat-teries(ZABs).Herein,we report the simple and environmentally-friendly fabrication of a single-atom Co electrocatalyst,Co-SA/N-C_(900),via in-suit pyrolysis of the co-precursor containing sucrose,dicyandiamide,and Co salts.The Co single atoms coordinated with adjacent N atoms are anchored on the doped ordered mesoporous carbon,generating the atomic Co-N_(4)moiety.Co-SA/N-C_(900)displays high oxygen reduction reaction(ORR)activity with an onset potential of 0.96 V and a half-wave potential of 0.87 V.Notably,the liquid ZAB with Co-SA/N-C_(900)catalyst exhibits exceptional discharge specific capacity of 706.38 mAh g^(-1),peak power density of 191.11 mW cm^(-2),and excellent stability at high current densities up to 100 mA cm^(-2),surpassing commercial Pt/C.According to the density functional theory(DFT)study,the Co-N_(4)moi-ety with graphitic N dopants can decrease the rate-determining step(RDS)energy barrier and thus accel-erate the ORR process.This study offers experimental and theoretical guidelines for the rational design of TM-N-C catalysts for practical implementation with notable ORR activity for application in ZABs.