基于氮掺杂碳载铁复合物的锌空电池氧阴极催化剂

迫在眉睫的环境和能源问题推动人类探索可行、可靠和可再生的能源技术.锌-空气电池和氢氧燃料电池等器件显示出高能量转换效率,但是仍有许多难题有待克服,例如阴极侧上缓慢的氧还原反应(ORR),以及高昂的成本极大地限制了铂基催化剂在商业上的广泛应用.因此,开发高性能的廉价ORR催化剂具有重要意义.过渡金属碳氮化合物(M-N-C, M=Co, Fe等)成为最有希望替代铂基催化剂的一类材料, M-N-C催化剂可以通过直接热解含有过渡金属、氮和碳物种的前驱体合成.然而热解时金属原子易团聚,多孔结构不能被有效地控制,导致相对较差的催化活性.目前, MOF衍生的催化剂在能源转化和储存技术中得到了广泛的关注,其具有丰富的氮含量、高比表面积和可调的孔道结构等特点.本文报道了一种简便可靠可控的合成铁氮共掺杂碳十二面体纳米结构催化剂的方法,并作为阴极电催化剂用于锌空气电池中,测试结果证实,合成的铁氮共掺杂的纳米碳具有与铂基材料相当的活性和更加优异的稳定性.表面吸附了的邻菲罗啉铁的ZIF-8在碳化过程中,氮基团能够结合铁形成Fe Nx结构单元,因此可得到铁氮共掺杂的电催化剂.粉末X射线衍射,扫描电镜证实ZIF-8的成功合成.经过热解得到的催化剂中Fe Nx或Fe Cx衍射峰较弱,表明样品中铁含量较低,存在部分无定型铁.通过拉曼光谱分析发现,引入的邻菲罗啉在热解过程中诱导了缺陷的形成,所以Fe-NCDNA-0的ID/IG比值明显高于NC.同时ID/IG随着铁含量的增加而减少,这是因为铁可以诱导石墨化,诱导效应随着铁含量的增加而增加.分析氮气吸附-脱附等温线得出,引入邻菲罗啉之后,比表面积增加;而铁的引入因其占据了微孔结构,导致比表面积下降.同时电镜证实Fe-NCDNA-2具有较大的形貌扭曲,使得该材料具有较大的比表面积.系统的电化学研究表明,氮掺杂有利于增强ORR活性,在引入铁之后形成高效的活性中心会进一步提高催化性能.因此, Fe-NCDNA-2在碱性条件下表现出优异的ORR性能.线性扫描伏安法曲线表明,铁氮共掺杂的材料表现出与Pt/C相似的性能,其中Fe-NCDNA-2的半波电位(E1/2)为0.863 V,比商业Pt/C的电位更正(E1/2=0.841 V).同时, Fe-NCDNA-2具有更加优异的稳定性,测试30000 s后的电流保持率为80%(Pt/C:64%).在中性介质中,合成的材料也展示了较高的ORR活性.Fe-NCDNA-2的E1/2=0.715 V,催化30000 s后电流保持率77%,均优于商业Pt/C催化剂.组装的锌空气电池进一步验证其作为氧还原催化剂实际应用的可行性.相比于以Pt/C为催化剂做空气阴极的电池,以Fe-NCDNA-2组装的电池表现出更高的开路电压,更高的功率密度(184 m Wcm^-2),以及更加优异的充放电循环稳定性.该工作也有利于启发研究人员探索类似的氮掺杂过渡金属碳材料在各种催化上的应用.     

Co9S8/MoS2异质结构的构筑及电催化析氢性能研究

利用前驱物形貌导向法,成功制备了Co₉S₈/MoS₂异质结构催化剂,该催化剂在碱性析氢反应（HER）中表现出优异的催化活性及稳定性,其在10 mA·cm^-2处的过电势仅为84 mV.通过X射线粉末衍射（XRD）、透射电子显微镜（TEM）、电子自旋共振（ESR）、拉曼光谱（Raman）、X射线光电子能谱（XPS）和同步辐射（XAFS）等表征,证明了CoS₂/MoS₂在H₂氛围下煅烧形成Co₉S₈/MoS₂的过程中,CoS₂中Co的配位模式从部分八面体向Co₉S₈中的四面体转变,这种转变可活化MoS₂的惰性平面,从而使其更有利于吸附H^*.除此之外,接触角数据表明：该催化剂具有良好的亲水性,有利于电解液渗透及气体分子的迅速扩散,从而促进HER反应速率.由于异质结构间具有强烈的相互作用,该催化剂可表现出良好的结构稳定性.本工作基于Co₉S₈/MoS₂异质结构的成功构筑及对其HER催化机理的充分探讨,为后续硫化物异质结及其在电催化中的应用提供了良好的思路和研究基础.     

Qualitative and quantitative analyses of aloe-emodin,rhein, and emodin in qi yin granules by high-performance thin-layer chromatography

The aim of this study was to perform qualitative and quantitative analyses of aloe-emodin, rhein, and emodin in three prepared samples of compound qi yin granules by high-performance thin-layer chromatography (HPTLC) and to establish an analytical method. TLC was used to qualitatively analyze the three major components of the compound: aloe-emodin, rhein, and emodin. HPTLC was performed to determine the contents of the three components. HPTLC analysis showed that using Anhui Liangchen high-efficiency silica gel G plate was the optimal stationary phase and the upper layer solution of a petroleum ether–ethyl acetate–formic acid (15.5:5:1, V/V) mixed solution was the optimal developing agent. The composition of the samples for testing was basically the same, but the content was different. In summary, this study used HPTLC to qualitatively and quantitatively analyze aloe-emodin, rhein, and emodin in compound qi yin granules. It can lay the foundation for improving the quality control and standards of compound qi yin granules.

     

Synthesis of CF2H‐Containing Oxime Ethers Derivatives from ClCF2H,tert‐Butyl Nitrile and Indoles

Summaryof main observation and conclusion A new and intriguing methodology to access various O-difluoromethylation oxime compounds from CICF2H,TBN and indoles is developed under mild reaction conditions.This strategy can suppress N-difluoromethylation of indoles successfully,in which there are two different active species(:CF2and·NO)while indoles are unprotected,featuringsimple operation and radical involvement.     

Palladium‐Catalyzed Asymmetric [4+3]‐Cyclization Reaction of Fused 1‐Azadienes with Amino‐trimethylenemethanes: Highly Stereoselective Construction of Chiral Fused Azepines

Summary of main observation and conclusion A Pd-catalyzed asymmetric aromative[4+3]-cyclization reaction of amino-trimethylenemethanes(TMM,1d,ip3-oles)with fused 1-azadienes has been developed.This method enables access to the synthetically importance and biologically active benzofuran fused azepines and indeno-azepines in excellent efficiency and stereoselectivity(up to 95%yield,99%ee,>19:1 dr).     

MALDI质谱技术在酶活性分析中的应用

酶作为生物催化剂参与很多重要的生理过程,同时也是一类重要的生物分子。酶的活性分析对于疾病诊断和治疗具有重要意义。基质辅助激光解吸电离飞行时间质谱(MALDI-TOF MS)具有操作简单、分析速度快、灵敏度高和易于实现高通量分析的特点,已被广泛用于各种组学研究和生物分子的检测,在酶的检测和活性分析中亦发挥了重要作用。该文综述了国内外利用MALDI-TOF MS分析酶活性和进行药物筛选的策略,总结了各种方法的优缺点,提出了MALDI质谱技术在酶活性分析领域存在的问题和挑战,并对其发展前景进行了展望。     

耐水钛系催化剂的合成及其在聚对苯二甲酸丁二醇酯合成中的应用

以钛酸四丁酯、柠檬酸或乳酸和氢氧化钾为原料在水中合成了一系列α-羟基酸钛催化剂,¹³C NMR、HR-MS(ESI)和元素分析表征。结果表明：α-羟基酸钛催化剂主要含柠檬酸或乳酸的α-羟基和α-羧基与钛离子形成的五元螯合环三配体配合物。其中,采用柠檬酸与TBT在氢氧化钾参与条件下制得的CTK-312催化剂,能够合成特性粘度高达1.268 dL·g^-1的PBT。      

无机纳米与多孔材料合成中的凝聚态化学

所谓凝聚态,一般意义上是指液态和固态,而凝聚态化学,即是在固相和液相中的各种化学过程。在无机材料,特别是无机纳米与多孔材料的合成制备中,凝聚态化学过程贯穿其中,几乎无处不在。在固相材料合成过程中,通过液相中的各种化学反应以获得目标固体材料的所需组分和物相,也许就是无机材料合成中一个最基本的凝聚态化学问题;而多孔如微孔或介孔材料合成中,更涉及伴随组分和物相形成过程中的孔结构形成与调控;进一步,在制备面向实际应用如催化剂和药物载体时,则在以上的各项要求之外,还必须考虑材料的表面活性位、缺陷等关键因素,以及颗粒尺寸、分散性和形貌等几何和物理特性。本文以无机氧化物为对象,讨论了无机材料在凝聚态化学合成过程中的几个侧面,包括纳米颗粒和粉体的化学合成方法,多孔材料的合成和多孔复相结构的合成调控,以及多级孔结构沸石的合成制备与催化性能,以期能加深对材料合成中凝聚态化学过程的认识,并期待以凝聚态化学为指导,进一步推动无机材料特别是纳米多孔材料合成的发展。     

Recent Advances in Atomic-scale Storage Mechanism Studies of Two-dimensional Nanomaterials for Rechargeable Batteries Beyond Li-ion

Developing new types of rechargeable batteries with high energy densities and low cost have received increasing attentions, aiming to reduce the dependence on high-priced lithium. Beyond Li-ion batteries, the potential alternatives including Na-ion batteries, Li-S batteries and Li-air batteries have been investigated recently, which are required to be viable for commercial applications. From this point of view, to understand the electrochemical reaction mechanisms and kinetics of these batteries has become the key challenge to make breakthroughs in the field of new energy storage. In this review, we present a critical overview of the two dimensional nanomaterials-based batteries (except Li-ion-based batteries) that could meet such demonds. To develop new energy storage devices with more promising performances, the microstructure evolution and atomic scale storage mechanism of these batteries are comprehensively summarized. In addition, the major challenges and opportunities of advanced characterization techniques are finally discussed. We do hope that this review will give the readers a clear and profound understanding of the electrochemical reaction mechanisms and kinetics of the as-discussed batteries, thus effectively contributing to the smart design of future-generation energy storage devices.     

Sorbents for the Direct Capture of CO2 from Ambient Air

The urgency to address global climate change induced by greenhouse gas emissions is increasing. In particular, the rise in atmospheric CO₂ levels is generating alarm. Technologies to remove CO₂ from ambient air, or “direct air capture” (DAC), have recently demonstrated that they can contribute to “negative carbon emission.” Recent advances in surface chemistry and material synthesis have resulted in new generations of CO₂ sorbents, which may drive the future of DAC and its large‐scale deployment. This Review describes major types of sorbents designed to capture CO₂ from ambient air and they are categorized by the sorption mechanism: physisorption, chemisorption, and moisture‐swing sorption.