Research Progress of Metal-Nitrogen-Carbon Catalysts toward Oxygen Reduction Reaction inm Changchun Institute of Applied Chemistry

氧还原反应是燃料电池的核心,开发高性能催化剂一直是燃料电池技术面临的严峻挑战. 近年来,热解M-N-C催化剂的发展和以金属有机骨架材料为前驱体的运用让非贵金属氧还原催化剂的性能大幅度提升,但催化活性位点、反应机理等方面仍不甚清晰,需要分子水平上进一步的研究. 在这里,作者总结了本课题组近些年来在氧还原方向上的研究成果,首先是对催化剂活性位点进行的相关探索,提出了新的活性位点结构,为开发新型催化剂提供了帮助,并对金属氮碳催化剂进行了细致的微观调控,探讨了最佳的合成方法;其次开发了高效的双原子Co2N5催化剂,并在理论计算的指导下合成出了更为高效的FeCo双原子催化剂,具备了替代铂基催化剂的性能;最后针对芬顿反应引发的稳定性问题而开发的低芬顿反应活性的单原子Cr和单原子Ru催化剂,表现出了较高的活性和稳定性,为解决催化剂实际应用问题开辟了新的研究思路与方向. 作者相信,通过对催化剂活性位点的不断认知和对新型催化剂的不断开发,终会让非贵金属催化的商业化应用成为现实.The development of highly active and stable catalysts toward oxygen reduction reaction (ORR) has been facing severe challenges. In recent years, pyrolytic M-N-C catalysts and metal-organic framework derived materials made the performance of non-noble metal catalysts greatly improved, however, the molecular and atomic level understanding in the reaction active sites and the mechanism are still lacking. Here, we summarize the recent research progress made in the Changchun Institute of Applied Chemistry. We present a microporous metal-organic-framework confined strategy toward the preferable formation of ORR catalysts. Firstly, we studied the active site and proposed a new active site structure for the Fe-N-C catalyst, which is helpful for the development of new catalyst. The M-N-C catalyst was carefully regulated and the best synthesis method was discussed; Secondly, a highly efficient binuclear Co2N5 catalyst was developed, which performs approximately 12 times higher activity than the conventional CoN4 site and shows unprecedented catalytic activity in an acidic electrolyte with the half-wave potential of 0.79 V, presenting the best one among the Co-N-C catalysts, and a more efficient FeCo diatomic catalyst was synthesized under the guidance of theoretical calculation, indicating that the FeCoN5—OH site enables the ORR onset potential and half-wave potential up to 1.02 and 0.86 V (vs. RHE), respectively, with an intrinsic activity over 20 times higher than the single-atom FeN4 site; Finally, to overcome the stability problem caused by Fenton reaction, we developed novel single atomic Cr and Ru catalysts, showing low Fenton reaction activity, higher activity and stability after the accelerated degradation test for 20000 cycles, with the half-wave potentials being dropped only 15 and 17 mV, respectively, much lower than 31 mV of Fe-N-C catalysts. This offers a new way to solve the problem in catalyst application. We believe that upon further understanding in the active sites and the continuous development of new catalyst, the non-noble metal catalysts in PEMFCs will become truly applicable, which aids to solve the increasingly serious energy crisis environment.国家重点研发计划项目(2017YFB0102900);国家自然科学基金(21633008);国家自然科学基金(21875243);国家自然科学基金(21433003);中国科学院战略重点研究先导项目(XDA09030104);RFBRprojectnumber(FateevVladimir)(18-53-53025);吉林省科技发展项目(20170520150JH);吉林省科技发展项目(20170203003SF);吉林省科技发展项目(20180101030JC)通讯作者:葛君杰,刘长鹏,邢巍E-mail:[email protected];[email protected];[email protected]:GEJun-jie,LIUChang-peng,XINGWeiE-mail:[email protected];[email protected];[email protected].中国科学院长春应用化学研究所,先进化学电源实验室,电分析化学国家重点实验室,吉林 长春 1300222.中国科学技术大学应用化学与工程学院,安徽 合肥 2300261. State Key Laboratory of Electroanalytica Chemistry, Changchun Institute of Applied Chemistry,Chinese Academy of Sciences University of Chinese Academy of Sciences, Changchun 130022,Jilin, China2. University of Science and Technology of China, School of Applied Chemistry & Engineering, Hefei 230026, Anhui, Chin

Acetylcholinesterase Biosensor Platform Based on BP2000 for the Detection of Carbaryl

为给农药西维因检测提供一种新方法，根据西维因抑制乙酰胆碱酯酶活性的原理，以黑珍珠2000（BP2000）为乙酰胆碱酯酶的固定化材料，采用滴凃电极法构建了基于乙酰胆碱酯酶的西维因生物传感平台. 结果表明，固定在BP2000 上的乙酰胆碱酯酶保持了对氯化乙酰胆碱的催化活性，并且由于BP2000 材料的引入，提升了电极有效的电化学活性表面积，而且电极上物质的电化学氧化拥有较低氧化电位（0.630 V）并伴随质子传输. 由BP2000 搭建成功的乙酰胆碱酯酶生物传感平台对西维因检测的线性响应范围为2.0 ng·mL-1 ~ 12.5 ng·mL-1，检测限为3.15 ng·mL-1. 本研究对酶生物传感平台和酶生物燃料电池体系中酶电极的构建提供了一种简单方法及高效载体.With the purpose of providing a new method for carbaryl (a pesticide) detection, on the basis of the principle that acetylcholinesterase (AChE) activity can be restrained by carbaryl, an AChE biosensor platform based on BP2000 (as a fixation) was constructed by dropping method. As a result, it revealed that AChE immobilized on BP2000 maintained its catalytic activity for acetylcholine (ATCl), and due to the introduction of the BP2000 material, the effective electrochemical surface area of the modified electrode was enlarged. In addition, the electrochemical oxidation at the modified electrode occurred at low potential (0.630 V) accompanied by proton transmission. The AChE biosensor platform based on BP2000 matrix for carbaryl detection was able to reflect a linear response in the range of 2.0 ng·mL-1 ~ 12.5 ng·mL-1 with the detection limit of 3.15 ng·mL-1. At last, this work will provide a simple method and an efficient matrix in establishing an enzyme electrode of enzymatic biosensor platform and enzymatic fuel cell.获2017年中国科学院大学生科创计划资助作者联系地址：1. 暨南大学化学与材料学院，广东 广州 511400；2. 中国科学院长春应用化学研究所，吉林省先进化学电源实验室，吉林长春 130022；3. 长春工程学院理学院；吉林长春 130012Author's Address: 1.College of Chemistry and Material Science, Jinan University, Guangzhou 511400, China; 2.Jilin Laboratory of Advanced Power, Changchun Institute of Applied Chemistry,Changchun 130022, China; 3.School of Science, Changchun Institute of Technology, Changchun 130012, Jilin, China.通讯作者E-mail：[email protected]

Research Progress in Hydrogen Evolution Low Noble/Non-Precious Metal Catalysts of Water Electrolysis

氢气作为能量载体的氢能技术由于其清洁性、高能量密度等优势已获得越来越多的青睐与关注. 其中，可持续的产氢技术是未来氢能经济发展的必要先决条件. 通过可再生资源电力驱动的电解水技术是支持氢能经济可持续发展的重要途径，高活性、低成本的析氢催化剂的开发利用是提高水电解技术效率并降低其成本的关键因素. 本文主要介绍了近年来包括低铂催化剂和金属硫化物、金属磷化物、金属硒化物等非铂过渡金属催化剂在析氢方面的研究进展，详细讨论了析氢反应的催化性能、合成方法以及结构?鄄催化性能的关系，最后总结展望了水电解低铂及非铂过渡金属催化剂在未来发展过程中所面临的机遇与挑战.Hydrogen energy technology with hydrogen as an energy carrier is gaining more and more attention due to its cleanliness and high energy density. Hydrogen fuel cell vehicles have been listed as one of the ultimate energy technologies in the 21st century. Among them, sustainable hydrogen production technology is a necessary prerequisite for the future development of hydrogen energy economy. Electrolyzed water technology driven by renewable resources represents an important way to support the sustainable development of hydrogen energy economy. The development and utilization of high activity, low cost hydrogen evolution catalysts is a key factor in improving the efficiency and reducing the cost of water electrolysis technology. This paper mainly introduces the recent research progress of hydrogen evolution catalysts including low platinum catalysts and non-platinum transition metal catalysts such as metal sulfides metal phosphides, metal selenides, etc; catalytic properties, synthesis methods, and structure-catalytic properties. Finally, the advantages and challenges of water electrolysis low platinum and non-platinum transition metal catalysts in the future development are prospected.国家自然科学基金(No. 21433003, No. 21733004)、中国科学院战略重点研究先导项目(No. XDA21090400, No. XDA09030104)、吉林省科技发展项目(No. 20180101030JC, No. 20170520150JH)和中国科学院百人计划项目资助作者联系地址：1.中国科学院长春应用化学研究所，电分析化学国家重点实验室，吉林省低碳化学电源重点实验室，吉林 长春130022；2.中国科学技术大学应用化学与工程学院，安徽 合肥 230026Author's Address: 1.State Key Laboratory of Electroanalytical Chemistry, Jilin Province Key Laboratory of Low Carbon Chemical Power Source, Changchun Institute of Applied Chemistry, Changchun 130022, China; 2.Shcool of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026, China通讯作者E-mail：[email protected]; [email protected]; [email protected]

Recent Progress in Non-Precious Metal Oxygen Reduction Reaction Catalysts with an Encapsulation Structure

燃料电池中广泛使用的铂基催化剂价格昂贵、储量低、容易失活，因此亟待开发廉价、高效非铂催化剂. 过渡金属(Fe、Co、Ni等)/杂原子共掺杂催化剂、杂原子掺杂（N、P、S、F等）碳材料以及碳材料包覆过渡金属复合物是目前发现的几类性能优异的非贵金属氧还原催化剂. 其中碳材料包覆过渡金属催化剂作为一类新型的高性能催化剂，对其研究还有待深入. 本文主要阐述了国内外在包覆型非贵金属氧还原催化剂方面的研究进展，从合成，性能，机理等方面对该类催化剂进行了总结，力求助益于该类催化剂的发展.Platinum-based materials, the state-of-the-art catalysts for fuel cells, suffer from prohibitive costs, limited resources and insufficient durability. Accordingly, tremendous efforts were made in searching for efficient, durable and inexpensive alternatives to precious-metal electrocatalysts for the oxygen reduction reaction (ORR). Transition-metals (Fe, Co)/nitrogen co-doped hybrids, heteroatom (N, P, S, F, et al) doped carbons and composites with transition-metals encapsulated in graphitic layers are reported as the most efficient non-precious metal ORR catalysts. Among the various non-precious metal ORR catalysts, transition-metals encased in graphitic layer catalysts are a novel type of catalysts for ORR with high activity and durability, and thus, the in-depth researches are highly desirable. Here, we present the recent research progress in transition-metals encased catalysts from the aspects of synthesis, activity and catalytic mechanism, in an effort to promote the developments of these catalysts.科技部973项目（No. 2012CB215500）、国家自然科学基金项目（No. 21373199，No. 21433003）、中国科学院先导专项（No. XDA09030104）、吉林省科技发展项目（No. 20130206068GX，No. 20140203012SF，No. 20102204）和吉林省自然科学基金项目（No. 20150101066JC）资助作者联系地址：1. 中国科学院长春应用化学研究所，电分析国家重点实验室，吉林 长春 130022；2. 中国科学院长春应用化学研究所，先进化学电源实验室，吉林 长春 130022Author's Address: 1. State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China; 2. Laboratory of Advanced Power Sources, Changchun Institute of Applied Chemistry, Changchun 130022, China通讯作者E-mail：[email protected]

Challenges in the Activity and Stability of Pt-Based Catalysts toward ORR

在质子交换膜燃料电池（PEMFC）中，由于阴极氧还原反应（ORR）速率缓慢，因此开发高效的ORR催化剂是实现燃料电池商业化的关键. 世界各地的研究人员在提高催化剂活性和耐久性方面做出了不懈的努力. 目前，铂基催化剂仍然是商业应用上的首选，为开发实用的低铂氧还原催化剂，研究人员开展了大量的研究. 本文说明了ORR反应遇到的挑战，并介绍了近年来铂基氧还原催化剂的研究进展，具体包括ORR机理、铂核壳结构、一维纳米Pt催化剂和其他的代表性工作.The development of highly efficient oxygen reduction reaction (ORR) catalysts is the key to the commercialization of fuel cells, where the sluggish ORR reaction rate needs to be overcome by adjusting the intermediates adsorption energies on the catalytic surfaces. To-date, platinum (Pt)-based materials are the-state-of-the-art catalysts in terms of both activity and stability in ORR, making them the preferred choice for commercial applications. However, the high cost of Pt-based catalysts limits their widespread use, leading to massive effects paid in reducing Pt loading, improving catalyst activity and stability. This article illustrates the challenges in the ORR reaction and introduces the recent research progresses in Pt-based oxygen reduction catalysts including the ORR mechanism, core-shell structures, one-dimensional nanostructure, and other representative works of Pt-based catalysts. Some perspectives in the future development trend of Pt-based catalysts are given at the end of the paper, hoping to provide readers with some ideological inspiration.国家重点研发计划项目（No. 2017YFB0102900）、国家自然科学基金（No. 21633008，No. 21875243，No. 21433003）、中国科学院战略重点研究先导项目（No. XDA09030104） 、俄罗斯基础研究基金会（18-53-53025，Fateev Vladimir）、吉林省科技发展项目（No. 20170520150JH，No. 20170203003SF，No. 20180101030JC）、中国科学院百人计划项目资助作者联系地址：1. 中国科学技术大学应用化学与工程学院，安徽 合肥 230026； 2. 中国科学院长春应用化学研究所，先进化学电源实验室，电分析化学国家重点实验室，吉林 长春 130022Author's Address: 1. School of Applied Chemistry and Engineering University of Science and Technology of China, Hefei 230026, Anhui ,China; 2. State Key Laboratory of Electroanalytica Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences University of Chinese Academy of Sciences,Changchun 130022, Jilin, China通讯作者E-mail：[email protected]; [email protected] ;[email protected]

Small-sized single-track travel mechanism

本实用新型涉及特种机器人的行走机构,具体地说是一种小型单轨道移动机构,包括底盘及两个相互独立、结构相同的转向架,每个转向架分别在轨道上运行,底盘分别与两个转向架相连;转向架包括驱动电机、固定架、主动行走轮、从动行走轮、导向轮及转盘,其中主动行走轮及从动行走轮相互独立、分别可转动地安装在固定架上,驱动电机固接在固定架上,主动行走轮与驱动电机的输出轴相连;在固定架的顶部设有转盘,底盘置于转盘上,转盘相对于底盘可转动,固定架的底部安装有多个导向轮。本实用新型适合各种弯轨形状,转弯半径小而灵活,转盘可相对于底盘有角度上的变化,避免移动机构自身干涉,实现了移动机构在各种弯道上的平稳运行

一种小型单轨道移动机构

Disclosed in the present invention is a moving mechanism of special robots, more specifically a small single-rail moving mechanism. The mechanism comprises a chassis (2) and two independent bogies (1) having the same structure, wherein each bogie (1) runs on a rail (3) independently, and the chassis (2) is connected with the two bogies (1) respectively the bogie (1) comprises a driving motor (4), a fixing frame (5), driving running wheels (6), slave running wheels (7), guide wheels (8) and a rotating disk (9), wherein the driving running wheels (6) and the slave running wheels (7) are independent of each other and are mounted on the fixing frame (5) respectively, the driving motor (4) is fixedly connected on the fixing frame (5), and the driving running wheels (6) is connected with the output shaft of the driving motor (4) the rotating disk (9) is provided on the top of the fixing frame (5). The chassis (2) is arranged on the rotating disk (9), and the rotating disk (9) can rotate relative to the chassis (2). Several guide wheels (8) are mounted on the bottom of the fixing frame (5). The small single-rail moving mechanism is suitable for a variety of shapes of curved rails, and its turning radius is small and flexible. The angle of the rotating disk (9) relative to the chassis (2) can be changed, so the interference within the moving mechanism is avoided, and the smooth running of the moving mechanism on variety kinds of curved rails can be realized.</p