Photo-generated dinuclear {Eu(II)}2 active sites for selective CO2 reduction in a photosensitizing metal-organic framework

利用太阳光驱动CO2还原不仅可降低大气中CO2浓度，而且可以生成重要的化工原料，是缓解气候变暖和开发新能源的理想途径之一。然而如何制备高效光催化剂将CO2高选择性地转化为高附加值的化学产品极具挑战性。课题组巧妙地将具有催化活性的稀土簇合物与光敏配体组装在一起，合成了具有大孔结构的稀土Eu-Ru(phen)3-MOF催化剂，实现了可见光驱动的CO2到甲酸盐的高效选择性转化。研究表明，该材料光催化生成甲酸盐的反应速率可达到321.9 μmol h−1 mmolMOF−1，这是至今为止报道的光催化还原CO2转化为甲酸盐活性最高的MOFs催化剂。 该项研究工作由博士生闫志浩完成，博士生杜明浩参与部分表征工作；中国科学院大连化学物理研究所金盛烨研究员、刘俊学博士在瞬态光谱表征中给予了支持；我校化学化工学院汪骋教授在数据分析过程中给予大量帮助；理论计算由浙江工业大学庄桂林副教授完成。【Abstract】Photocatalytic reduction of CO2 is a promising approach to achieve solar-to-chemical energy conversion. However, traditional catalysts usually suffer from low efficiency, poor stability, and selectivity. Here we demonstrate that a large porous and stable metal-organic framework featuring dinuclear Eu(Ⅲ)2 clusters as connecting nodes and Ru(phen)3 -derived ligands as linkers is constructed to catalyze visible-light-driven CO2 reduction. Photo-excitation of the metalloligands initiates electron injection into the nodes to generate dinuclear {Eu(Ⅱ)} 2 active sites, which can selectively reduce CO2 to formate in a two-electron process with a remarkable rate of 321.9μmolh −1 mmol MOF −1 . The electron transfer from Ru metalloligands to Eu(Ⅲ)2 catalytic centers are studied via transient absorption and theoretical calculations, shedding light on the photocatalytic mechanism. This work highlights opportunities in photo- generation of highly active lanthanide clusters stabilized in MOFs, which not only enables efficient photocatalysis but also facilitates mechanistic investigation of photo-driven charge separation processes.We are grateful for the financial support from the 973 project (Grant 2014CB845601) of the Ministry of Science and Technology of China, the National Natural Science Foundation of China (Grants no. 21422106, 21673184, 21431005, 21721001, and 21390391) and the Fok Ying Tong Education Foundation (151013). We thank Dr. Wen-Ming Qin and the staffs from the BL17B beamline of National Center for Protein Sciences Shanghai at Shanghai Synchrotron Radiation Facility for assistance during data collection; we also thank Miss Ying-Zi Han for helpful measurement on ESI-MS. We also gratefully acknowledge Mr Xuefu Hu for helpful measurement on time-resolved PL and Miss Rong Chen for her assistance on CV measurement and analysis. 研究工作得到科技部（项目批准号：2014CB845601）、国家自然科学基金委（项目批准号：21422106、21673184、21431005、21721001、21390391）、教育部霍英东基金会青年教师基金（项目批准号：151013）等资助

Effect of lanthanide contraction on crystal structures of lanthanide coordination polymers with 2,5-piperazinedione-1,4-diacetic acid

通讯作者地址: Kong, XJ (通讯作者), Xiamen Univ, State Key Lab Phys Chem Solid Surface, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China 地址: 1. Xiamen Univ, State Key Lab Phys Chem Solid Surface, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China 2. Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China 电子邮件地址: [email protected] series of lanthanide coordination polymers have been synthesized through the hydrothermal reaction of 2,5-piperazinedione-1,4-diacetic acid (H2PODC) and Ln(NO3)(3) (Ln = La, 1; Pr, 2; Sm, 3; Ho, 4 and Er, 5). Crystal structure analysis reveals that their structural variations are attributed to the effect of lanthanide contraction.NNSFC 20825103 20721001 20901064 MSTC 2007CB815304 Natural Science Foundation of Fujian Province of China 2008J001

Synthesis, Electrical/Magnetic Properties of Amino Acid Derivatives-Based Rare-Earth Complexes

自从十九世纪末A.Werner创立配位化学以来，配位化学已经有一百多年的发展历史。当前配位化合物在配位化学、固体化学、材料化学、晶体工程、超分子化学等诸多领域成为广泛研究的热点，是无机化学研究最为活跃的领域之一。构筑单元的多样化，以配位键为主，分子间作用力或者主客体相互作用为辅的组装方式赋予配位化合物具有丰富迷人的结构和广阔潜在的应用前景。 作为配合物的一个分支，稀土配合物不仅拥有精彩纷呈的拓扑结构，而且还表现出光、电、磁、催化和吸附等奇特的物理和化学性质。然而比起欣欣向荣的过渡金属配合物的研究，稀土配合物在结构的精确预测和定向组装、性质的可调控性以及复合功能材料的研究还相对滞后。本论文正是...Since the coordination chemistry was founded by A. Werner in the late nineteenth century, it has developed for more than one hundred years. Recently, the researches of complex have become one of the most active fields of inorganic chemistry.and attracted numerous attentions in the field of coordination chemistry, solid chemistry, material chemistry, supramolecure chemistry, crystal engineering, et...学位：理学博士院系专业：化学化工学院化学系_无机化学学号：1912005140304

溶剂对呋喃二羧酸与Mn(Ⅱ)自组装的结构调控(英文)

以呋喃二羧酸(H2FDC)与Mn(Ⅱ)为研究对象,通过改变体系溶剂分别得到了化合物Mn(FDC).(H2O)3(1)和化合物[H2N(CH3)2]2.[Mn3(FDC)4].2DMF.H2O(2).当反应溶剂为N,N'-二甲基甲酰胺(DMF)与水的混合溶剂时,形成了具有一维链状结构的化合物1,而当反应溶剂为N,N'-二甲基甲酰胺时,形成了具有三维开放结构的化合物2,体现了溶剂对产物结构的影响.变温磁化率测试及量子蒙特卡洛方法拟合都表明,化合物1和2均具有反铁磁性

Review on astaxanthin production from agricultural wastes by Phaffia rhodozyma

Astaxanthin production by Phaffia rhodozyma is environmentally friendly, safe, and cost effect, but the cost of the medium for culture of Phaffia rhodozyma especially carbon sources is one of the major factors that constrain this process from achieving m

利用农业废弃物碳源的红法夫酵母生产虾青素研究进展

利用红法夫酵母产虾青素工艺具有绿色、安全、低成本等优点,但培养红法夫酵母的培养基（尤其是碳源）成本是制约该工艺实现大规模生产的主要因素之一。传统的利用纯糖如葡萄糖、蔗糖、木糖等作为红法夫酵母生产虾青素的碳源,效果虽好,但因其价格较高,仅适用于实验室研究和小型发酵生产,不适于大规模工业化生产。如何寻找来源广、价廉且发酵效果好的碳源,降低虾青素的生产成本是发展虾青素产业亟待解决的课题。利用廉价且来源广泛的原料如水果类原料、糖质原料、甘油及废弃木质纤维素类原料等作为碳源能有效降低成本。但这些原料都存在一些问题,比如水果类原料存在季节性及地域性限制,糖蜜类原料供应稳定性方面存在问题,甘油类原料杂质多且存在食品安全隐患,木质纤维素类原料来源广泛、价格低廉,不存在占用耕地等问题,是最有希望用于规模化低成本发酵生产虾青素的原料,但其利用存在一些技术瓶颈。该文介绍了目前利用红法夫酵母生产虾青素的基本情况,并系统地对国内外不同碳源条件下利用红法夫酵母生产虾青素的研究状况进行了综述、比较及分析。最后,对利用红法夫酵母生产虾青素在碳源方面的未来发展趋势及重点研究方向进行了展望

The synthesis of a 3d-4f polynuclear metal cluster under microwave irradiation: crystal structure and magnetic property of [La3Ni6(IDA)(6)(OH)(6)(H2O)(12)]center dot 3NO(3)center dot 15H(2)O (IDA = iminodiacetate)

通讯作者地址: Long, LS (通讯作者), Xiamen Univ, State Key Lab Phys Chem Solid Surface, Xiamen 361005, Peoples R China 地址: 1. Xiamen Univ, State Key Lab Phys Chem Solid Surface, Xiamen 361005, Peoples R China 2. Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China 电子邮件地址: [email protected] 3d-4f heterometallic ferromagnetic cluster, consisting of six Ni(II) and three La(III) ions, was synthesized by microwave irradiation. Themagnetic susceptibilities of the cluster were fitted with the help of the program MAGPACK, revealing that the magnetic exchange in the cluster is closely related to the coordination mode and spatial distribution between the metal ions.NNSFC 20825103 20721001 973 project 2007CB815304 MSTC Natural Science Foundation of Fujian Province of China 2008J001

JUNO Sensitivity on Proton Decay p→νˉK+p\to \bar\nu K^+ Searches

The Jiangmen Underground Neutrino Observatory (JUNO) is a large liquid scintillator detector designed to explore many topics in fundamental physics. In this paper, the potential on searching for proton decay in $p\to \bar\nu K^+$ mode with JUNO is investigated.The kaon and its decay particles feature a clear three-fold coincidence signature that results in a high efficiency for identification. Moreover, the excellent energy resolution of JUNO permits to suppress the sizable background caused by other delayed signals. Based on these advantages, the detection efficiency for the proton decay via $p\to \bar\nu K^+$ is 36.9% with a background level of 0.2 events after 10 years of data taking. The estimated sensitivity based on 200 kton-years exposure is $9.6 \times 10^{33}$ years, competitive with the current best limits on the proton lifetime in this channel

JUNO sensitivity on proton decay p → ν K + searches*

The Jiangmen Underground Neutrino Observatory (JUNO) is a large liquid scintillator detector designed to explore many topics in fundamental physics. In this study, the potential of searching for proton decay in the $p\to \bar{\nu} K^+$ mode with JUNO is investigated. The kaon and its decay particles feature a clear three-fold coincidence signature that results in a high efficiency for identification. Moreover, the excellent energy resolution of JUNO permits suppression of the sizable background caused by other delayed signals. Based on these advantages, the detection efficiency for the proton decay via $p\to \bar{\nu} K^+$ is 36.9% ± 4.9% with a background level of $0.2\pm 0.05({\rm syst})\pm$$0.2({\rm stat})$ events after 10 years of data collection. The estimated sensitivity based on 200 kton-years of exposure is $9.6 \times 10^{33}$ years, which is competitive with the current best limits on the proton lifetime in this channel and complements the use of different detection technologies