腐殖酸与金属离子Fe3+\Cu2+\Al3+配位电荷传输特性的理论研究

摘要
图/表
参考文献
相关文章 (15)

全文: PDF (473 KB) HTML (1 KB)
输出: BibTeX | EndNote (RIS)

摘要

腐殖酸是细胞外电子受体的重要组成部分。实验研究表明，与不同金属元素配位的腐殖酸分子具有不同的电子接受能力。本文采用密度泛函理论，选择腐殖酸(LHA)有机大分子作为配体，研究了配体与不同金属的相互作用。同时，计算了键能，分析了复合物的结构特征和前线分子轨道。在马库斯理论的基础上，计算了重组能、矩阵元素和电荷传输速率常数。研究结果表明，不同金属配合物的电荷传输速率顺序为Fe3+ > Cu2+ > Al3+，与实验结果吻合较好。

	服务

	把本文推荐给朋友
	加入我的书架
	加入引用管理器
	E-mail Alert
	RSS
	作者相关文章
	罗慧
	陈晓
	刘柳斜
	张明
	李来才
	田安明

关键词 ： charge transport, density functional theory, humic acid, Marcus theory

Abstract：

Humic acid is a key component of extracellular electron acceptor. Experimental study elucidates that humic acid molecular ligand with different metal elements has different abilities to accept electrons. By using density functional theory, this article selected the leonardite humic acid (LHA) organic macromolecule as ligand to study interactions between the ligand and different metals. At the same time, the calculation of binding energy, the analysis of characteristics for the complex structure and the distribution of frontier molecular orbital were also completed. On the basis of Marcus theory, the reorganization energy, matrix element and charge transport rate constant were calculated. The results show that the order of the charge transfer rates is Fe3+ > Cu2+ > Al3+ for different metal complexes, and are in good agreement with the experimental ones.

Key words： charge transport density functional theory humic acid, Marcus theory

收稿日期: 2018-04-24 出版日期: 2019-03-12

基金资助:

This project was supported by the Sichuan Province Department Education (13ZA0150) and the Sichuan Province (2014JY0099)

通讯作者: lilcmail@163.com E-mail: lilcmail@163.com

引用本文:

罗慧;陈晓;刘柳斜;张明;李来才;田安明. 腐殖酸与金属离子Fe3+\Cu2+\Al3+配位电荷传输特性的理论研究[J]. 结构化学, 2019, 38(3): 439-447.
LUO Hui;CHEN Xiao;LIU Liu-Xie;ZHANG Ming;LI Lai-Cai;TIAN An-Ming. Theoretical Researches on the Charge Transport Properties of Humic Acid Coordinating with Fe³⁺\Cu²⁺\Al³⁺ Metal Ions. CHINESE JOURNAL OF STRUCTURAL CHEMISTRY, 2019, 38(3): 439-447.

链接本文:

http://manu30.magtech.com.cn/jghx/CN/ 或 http://manu30.magtech.com.cn/jghx/CN/Y2019/V38/I3/439

REFERENCES
(1) Pan, G. X.; Li, L. Q.; Wu, L. S.; Zhang, X. H. Storage and sequestration potential of topsoil organic carbon in China's paddy soils. Global Change Biol. 2003, 10, 7992.
(2) Conrad, R. Contribution of hydrogen to methane production and control of hydrogen concentrations in methanogenic soils and sediments. FEMS Microbiol. Ecol. 1999, 28, 193202.
(3) Lovley, D. R.; Coates, J. D.; Blunt-Harris, E. L.; Phillips, E. J. P.; Woodward, J. C. Humic substances as electron acceptors for microbial respiration. Nature 1996, 382, 445448.
(4) Heitmann, T.; Blodau, C. Oxidation and incorporation of hydrogen sulfide by dissolved organic matter. Chem. Geol. 2006, 235, 1220.
(5) Keller, J. K.; Weisenhorn, P. B.; Megonigal, J. P. Humic acids as electron acceptors in wetland decomposition. Soil Biol. Biochem. 2009, 41, 15181522.
(6) Coates, J. D.; Cole, K. A.; Chakraborty, R.; O’Connor, S. M.; Achenbach, L. A. Diversity and ubiquity of bacteria capable of utilizing humic substances as electron donors for anaerobic respiration. Appl. Environ. Microbiol. 2002, 68, 24452452.
(7) Minderlein, S.; Blodau, C. Humic-rich peat extracts inhibit sulfate reduction, methanogenesis, and anaerobic respiration but not acetogenesis in peat soils of a temperate bog. Soil Biol. Biochem. 2010, 42, 20782086.
(8) Bauer, I.; Kappler, A. Rates and extent of reduction of Fe(III) compounds and O2 by humic substances. Environ. Sci. Technol. 2009, 43, 49024908.
(9) Maurer, F.; Christl, I.; Fulda, B.; Voegelin, A.; Kretzschmar, R. Copper redox transformation and complexation by reduced and oxidized soil humic acid. 2. Potentiometric titrations and dialysis cell experiments. Environ. Sci. Technol. 2013, 47, 1091210921.
(10) Fulda, B.; Voegelin, A.; Maurer, F.; Christl, I.; Kretzschmar, R. Copper redox transformation and complexation by reduced and oxidized soil humic acid. 1. X-ray absorption spectroscopy study. Environ. Sci. Technol. 2013, 47, 1090310911.
(11) Zhou, S. G.; Chen, S. S.; Yuan, Y.; Lu, Q. Influence of humic acid complexation with metal ions on extracellular electron transfer activity. Scientific Reports 2015, 5, 17067.
(12) Yan, M. Q.; Korshin, G. V. Comparative examination of effects of binding of different metals on chromophores of dissolved organic matter. Environ. Sci. Technol. 2014, 48, 31773185.
(13) Yang, L.; Wei, Z. G.; Zhong, W. H.; Cui, J.; Wei, W. Modifying hydroxyapatite nanoparticles with humic acid for highly effcient removal of Cu(II) from aqueous solution. Colloids and Surfaces A 2016, 490, 921.
(14) Kappler, A.; Benz, M.; Schink, B.; Brune, A. Electron shuttling via humic acids in microbial iron(III) reduction in a freshwater sediment. FEMS Microbiol. Ecol. 2004, 47, 8592.
(15) Niederer, C.; Gossl, K. U. Quantum chemical modeling of humic acid/air equilibrium partitioning of organic vapors. Environ. Sci. Technol. 2007, 41, 36463652.
(16) Nuerla, A. L. J.; Qiao, X. L.; Li, J.; Zhao, D. M.; Yang, X. H.; Xie, Q.; Chen, J. W. Effects of substituent position on the interactions between PBDEs/PCBs and DOM. Chin. Sci. Bull. 2012, 57, 32653271.
(17) Liu, J.; Chakraborty, S.; Hosseinzadeh, P.; Yu, Y.; Tian, S.; Petrik, I.; Bhagi, A.; Lu, Y. Metalloproteins containing cytochrome, iron-sulfur, or copper redox centers. Chem. Rev. 2014, 114, 43664469.
(18) Cornil, J.; Lemaur, V.; Calbert, J. P.; Brédas, J. L. Charge transport in discotic liquid crystals: a molecular scale description. Adv. Mater. 2002, 14, 726729.
(19) Balzani, V.; Juris, A.; Venturi, M.; Campagna, S.; Serroni, S. Luminescent and redox-active polynuclear transition metal complexes. Chem. Rev. 1996, 96, 759833.
(20) Jin, R. F.; Wang, F. X.; Guan, R. J.; Zheng, X. M.; Zhang, T. Design of perylene-diimides-based small-molecules semiconductors for organic solar cells. Mol. Phys. 2017, 115, 15911597.
(21) Ma, C. H.; Liang, W.; Jiang, D. Y.; Hong, Z.; Qing, L.; Yan, Y. S. Theoretical study of the photophysical and charge transport properties of novel fluorescent fluorine-boron compounds. Mol. Phys. 2010, 108, 667674.
(22) Chen, X. K.; Zou L. Y.; Fan, J. X.; Zhang, S. F.; Ren, A. M. Effect of dihydropyrazine on structures and charge transport properties of N-heteropentacenes matters: a theoretical investigation. Org. Electron. 2012, 13, 28322842.
(23) Jones, L.; Lin, L. A theoretical study on the isomers of the B5TB heteroacene for improved semiconductor properties in organic electronics. Comput. Theor. Chem. 2017, 1115, 22–29.
(24) Coropceanu, V.; Cornil, J.; Filho, D. A. S.; Olivier, Y.; Silbey, R.; Brédas, J. L. Charge transport in organic semiconductors. Chem. Rev. 2007, 107, 926952.
(25) Yin, J.; Chen, R. F.; Zhang, S. L. Theoretical study of charge-transfer properties of the π-stacked poly(1,1-silafluorene)s. J. Phys. Chem. C 2011, 115, 1477814785.
(26) Shin, M. W.; Lee, H. C.; Kim, K. S.; Lee, S. H.; Kim, J. C. Thermal analysis of tris(8-hydroxyquinoline) aluminum. Thin Solid Films 2000, 363, 244247.
(27) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery Jr. , J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Keith, T.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian Inc., Wallingford CT 2009, Gaussian 09, Revision A. 02.
(28) Becke, A. D. Density-functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 1993, 98, 56485652.
(29) Miehlich, B.; Savin, A.; Stoll, H.; Preuss, H. Results obtained with the correlation energy density functionals of Becke and Lee, Yang and Parr. Chem. Phys. Lett. 1989, 157, 200206.
(30) Lee, C.; Yang, W. T.; Parr, R. G. Development of the colle-salvetti correlation-energy formula into a functional of the electron density. Phys. Rev. B 1988, 37, 785789.
(31) Boys, S. F.; Bernardi, F. The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors. Mol. Phys. 1970, 19, 553566.
(32) Scalmani, G.; Frisch, M. J. Continuous surface charge polarizable continuum models of solvation. I. General formalism. J. Chem. Phys. 2010, 132, 114110.