Citation: Ya-Xiang SHI, Wen-Da ZHANG, Xin FANG, Xiao-Dong YAN, Zhi-Guo GU. Binuclear Iron Oxime Boric Acid Based Metal-Containing Porous Organic Polymer: Synthesis, Structure and Electrocatalytic Oxygen Evolution Properties[J]. Chinese Journal of Inorganic Chemistry, ;2021, 37(12): 2193-2202. doi: 10.11862/CJIC.2021.249 shu

Binuclear Iron Oxime Boric Acid Based Metal-Containing Porous Organic Polymer: Synthesis, Structure and Electrocatalytic Oxygen Evolution Properties

School of Chemistry and Material Engineering, Jiangnan University, Wuxi, Jiangsu 214122, China

Corresponding author: Zhi-Guo GU, zhiguogu@jiangnan.edu.cn
Received Date: 18 June 2021
Revised Date: 27 September 2021

Figures(8)

A three-dimensional metal-containing porous organic polymer (Fe₂-POP) was synthesized using ferrous chloride, 2, 6-diformyl-4-methylphenol dioxime (H₃DFMP) and tetra(4-(dihydroxy)borylphenyl)methane (TBPM) through one-step coordination and boric acid esterification dehydration polymerization reaction. Binuclear iron as the linear unit was formed by coordination between iron ion and H₃DFMP, while TBPM was used as the tetrahedral linking unit, so that the three-dimensional porous organic polymer Fe₂-POP with dia topology was produced. X-ray single crystal diffraction analysis of the model compound (MC-1) verified the structural characteristics of the dinuclear ferrous unit. Infrared spectroscopy and solid-state nuclear magnetism characterizations proved the formation of C=N and B-O in Fe₂-POP. Fe₂-POP had a high specific surface area of 510 m²·g^-1 and uniform pore size (0.6-0.8 nm). X-ray photoelectron spectroscopy indicated the presence of divalent iron in Fe₂-POP. Scanning electron microscopy and transmission electron microscopy showed that Fe₂-POP was composed of 50-100 nm sphere-shaped particles. Electrochemical tests showed that Fe₂-POP exhibited excellent electrochemical properties towards oxygen evolution reaction, and it only needed a small overpotential of 258 mV to deliver a current density of 10 mA·cm^-2, and the Tafel slope was 71.0 mV·dec^-1.
- binuclear iron,
- porous organic polymers,
- boric acid esterification dehydration polymerization,
- electrocatalysis,
- oxygen evolution reaction
1. [1]
  Guo X X, Kong R M, Zhang X P, Du H T, Qu F L. Ni(OH)₂ Nanoparticles Embedded in Conductive Microrod Array: An Efficient and Durable Electrocatalyst for Alkaline Oxygen Evolution Reaction[J]. ACS Catal., 2017,8(1):651-655.
2. [2]
  Cui X, Lei S, Wang A C, Gao L K, Zhang Q, Yang Y K, Lin Z Q. Emerging Covalent Organic Frameworks Tailored Materials for Electrocatalysis[J]. Nano Energy, 2020,70:2211-2855.
3. [3]
  Zhao J, Zhang J J, Li Z Y, Bu X H. Recent Progress on NiFe-Based Electrocatalysts for the Oxygen Evolution Reaction[J]. Small, 2020,16(51)e2003916. doi: 10.1002/smll.202003916
4. [4]
  Suen N T, Hung S F, Quan Q, Zhang N, Xu Y J, Chen H M. Electrocatalysis for the Oxygen Evolution Reaction: Recent Development and Future Perspectives[J]. Chem. Soc. Rev., 2017,46(2):337-365. doi: 10.1039/C6CS00328A
5. [5]
  Oscar D M, Isis L Y, Koper T M, Federico C V. Guidelines for the Rational Design of Ni-Based Double Hydroxide Electrocatalysts for the Oxygen Evolution Reaction[J]. ACS Catal., 2015,5(9):5380-5387. doi: 10.1021/acscatal.5b01638
6. [6]
  Wu Z P, Lu X F, Zang S Q, Lou X W. Non-Noble-Metal-Based Electrocatalysts toward the Oxygen Evolution Reaction[J]. Adv. Funct. Mater., 2020,30(15)1910274. doi: 10.1002/adfm.201910274
7. [7]
  Slater A G, Cooper A I. Function-Led Design of New Porous Materials[J]. Science, 2015,348(6238)aaa8075. doi: 10.1126/science.aaa8075
8. [8]
  Das S, Heasman P, Ben T, Qiu S L. Porous Organic Materials: Strategic Design and Structure-Function Correlation[J]. Chem. Rev., 2017,117(3):1515-1563. doi: 10.1021/acs.chemrev.6b00439
9. [9]
  Jin H Y, Guo C X, Liu X, Liu J L, Vasileff A, Jiao Y, Zheng Y, Qiao S Z. Emerging Two-Dimensional Nanomaterials for Electrocatalysis[J]. Chem. Rev., 2018,118(13):6337-6408. doi: 10.1021/acs.chemrev.7b00689
10. [10]
  Li Z E, He T, Gong Y F, Jiang D L. Covalent Organic Frameworks: Pore Design and Interface Engineering[J]. Acc. Chem. Res., 2020,53(8):1672-1685. doi: 10.1021/acs.accounts.0c00386
11. [11]
  Xu Y H, Jin S B, Xu H, Atsushi N, Jiang D L. Conjugated Microporous Polymers: Design, Synthesis and Application[J]. Chem. Soc. Rev., 2013,42(20):8012-8031. doi: 10.1039/c3cs60160a
12. [12]
  Dong J Q, Han X, Liu Y, Li H Y, Cui Y. Metal-Covalent Organic Frameworks (MCOFs): A Bridge between Metal-Organic Frameworks and Covalent Organic Frameworks[J]. Angew. Chem. Int. Ed., 2020,59(33):13722-13733. doi: 10.1002/anie.202004796
13. [13]
  Bhat S A, Das C, Maji T K. Metallated Azo-Naphthalene Diimide Based Redox Active Porous Organic Polymer as an Efficient Water Oxidation Electrocatalyst[J]. J.Mater.Chem.A, 2018,6(40):19834-19842. doi: 10.1039/C8TA06588H
14. [14]
  Jia H K, Yao Y C, Gao Y Y, Lu D P, Du P W. Pyrolyzed Cobalt Porphyrin-Based Conjugated Mesoporous Polymers as Bifunctional Catalysts for Hydrogen Production and Oxygen Evolution in Water[J]. Chem. Commun., 2016,52(92):13483-13486. doi: 10.1039/C6CC06972J
15. [15]
  Guan X Y, Chen F Q, Fang Q R, Qiu S L. Design and Applications of Three Dimensional Covalent Organic Frameworks[J]. Chem. Soc. Rev., 2020,49(5):1357-1384. doi: 10.1039/C9CS00911F
16. [16]
  Dolganov A V, Belov A S, Novikov V V, Vologzhanina A V, Mokhir A, Bubnov Y N, Voloshin Y Z. Iron vs. Cobalt Clathrochelate Electrocatalysts of HER: The First Example on a Cage Iron Complex[J]. Dalton. Trans., 2013,42(13):4373-4376.
17. [17]
  Dolganov A V, Tarasova O V, Ivleva A Y, Chernyarva O Y, Grigoryan K A, Ganz V S. Iron(Ⅱ) Clathrochelates as Electrocatalysts of Hydrogen Evolution Reaction at Low pH[J]. Int. J. Hydrog. Energy, 2017,42(44):27084-27093. doi: 10.1016/j.ijhydene.2017.09.080
18. [18]
  Cheikh J A, Villagra A, Ranjbari A, Pradon A, Antuch M, Dragoe D, Millet P, Assaud L. Engineering a Cobalt Clathrochelate/Glassy Carbon Interface for the Hydrogen Evolution Reaction[J]. Appl. Catal. B, 2019,250:292-300. doi: 10.1016/j.apcatb.2019.03.036
19. [19]
  Bila J L, Marmier M, Zhurov K O, Scopelliti R, Zivkovic I, Ronnow H M, Shaik N E, Sienkiewicz A, Fink C, Severin K. Homo- and Heterodinuclear Iron Clathrochelate Complexes with Functional Groups in the Ligand Periphery[J]. Eur. J. Inorg. Chem., 2018,26:3118-3125.
20. [20]
  Sumit K, Thomas W, Eckhard B, Phalguni C. Deliberate Synthesis for Magnetostructural Study of Linear Tetranuclear Complexes B^ⅢMn^ⅡMn^ⅡB^Ⅲ, Mn^ⅢMn^ⅡMn^ⅡMn^Ⅲ, Mn^ⅣMn^ⅡMn^ⅡMn^Ⅳ, Fe^ⅢMn^ⅡMn^ⅡFe^Ⅲ, and Cr^ⅢMn^ⅡMn^ⅡCr^Ⅲ Influence of Terminal Ions on the Exchange Coupling[J]. Inorg. Chem., 2006,45:5911-5923. doi: 10.1021/ic060409a
21. [21]
  SAINT-Plus, Version 6.02, Bruker Analytical X-ray System, Madison, WI, 1999.
22. [22]
  Sheldrick G M. Bruker Analytical X-ray Systems, Madison, WI, 1996.
23. [23]
  (a) Sheldrick G M. SHELXTL-97, Program for X-ray Crystal Structure Solution and Refinement, Universität of Göttingen, Göttingen, Germany, 1997.
  (b)Sheldrick G M. A Short History of SHELX. Acta Crystallogr. Sect. A: Found. Crystallogr., 2008, 64(1): 112-122
24. [24]
  Fang Q R, Wang J H, Gu S, Kaspar R B, Zhuang Z B, Zheng J, Guo H X, Qiu S L, Yan Y S. 3D Porous Crystalline Polyimide Covalent Organic Frameworks for Drug Delivery[J]. J. Am. Chem. Soc., 2015,137(26):8352-8355. doi: 10.1021/jacs.5b04147
25. [25]
  Ma Y X, Li Z J, Wei L, Ding Y B, Wang W. A Dynamic Three-Dimensional Covalent Organic Framework[J]. J. Am. Chem. Soc., 2017,139(14):4995-4998. doi: 10.1021/jacs.7b01097
26. [26]
  Wu C Y, Liu Y M, Liu H, Duan C H, Pan Q Y, Zhu J, Hu F, Ma X Y, Jiu T G, Li Z B, Zhao Y J. Highly Conjugated Three-Dimensional Covalent Organic Frameworks Based on Spirobifluorene for Perovskite Solar Cell Enhancement[J]. J. Am. Chem. Soc., 2018,140(3):10016-10024.
27. [27]
  Bila, Marmier, Zhurov, Scopelliti, Zickovic, Ronnow, Shalk, Sienkiewicz, Cornel, Severin. Homo- and Heterodinuclear Iron Clathrochelate Complexes with Functional Groups in the Ligand Periphery[J]. Eur. J. Inorg. Chem., 2018,26:3118-3125.
28. [28]
  Capon J F, Gloaguen F, Schollhammer P, Talarmin J. Catalysis of the Electrochemical H 2 Evolution by Di-iron Sub-site Models[J]. Coord. Chem. Rev., 2005,249(15/16):1664-1676.
29. [29]
  Lu H, Wang C, Chen J J, Ge R, Leng W G, Dong B, Huang J, Gao Y N. A Novel 3D Covalent Organic Framework Membrane Grown on a Porous α-Al₂O₃ Substrate under Solvothermal Conditions[J]. Chem. Commun., 2015,51(85):15562-15565. doi: 10.1039/C5CC06742A
30. [30]
  Alameddine B, Shetty S, Baig N, Saleh A M, Fakhreia A S. Synthesis and Characterization of Metalorganic Polymers of Intrinsic Microporosity Based on Iron(Ⅱ) Clathrochelate[J]. Polymer, 2017,122:200-207. doi: 10.1016/j.polymer.2017.06.048
31. [31]
  Long X, Li J K, Xiao S, Yan K Y, Wang Z L, Chen H N, Yang S H. A Strongly Coupled Graphene and FeNi Double Hydroxide Hybrid as an Excellent Electrocatalyst for the Oxygen Evolution Reaction[J]. Angew. Chem. Int. Ed., 2014,53(29):7584-7588. doi: 10.1002/anie.201402822
32. [32]
  Babar P T, Pawar B S, Lokhande A C, Gang M G, Jang J S, Suryawanshi M P, Pawar S M, Kim J H. Annealing Temperature Dependent Catalytic Water Oxidation Activity of Iron Oxyhydroxide Thin Films[J]. J. Energy Chem., 2017,26(4):757-761. doi: 10.1016/j.jechem.2017.04.012
33. [33]
  Lee J Y, Lee H Y, Lim B K. Chemical Transformation of Iron Alkoxide Nanosheets to FeOOH Nanoparticles for Highly Active and Stable Oxygen Evolution Electrocatalysts[J]. J. Ind. Eng. Chem., 2018,58:100-104. doi: 10.1016/j.jiec.2017.09.013
34. [34]
  Yu L, Yang J F, Guan B Y, Lu Y, Lou W D. Hierarchical Hollow Nanoprisms Based on Ultrathin Ni-Fe Layered Double Hydroxide Nanosheets with Enhanced Electrocatalytic Activity towards Oxygen Evolution[J]. Angew. Chem. Int. Ed., 2018,57(1):172-176. doi: 10.1002/anie.201710877
35. [35]
  Gu M L, Wang S C, Chen C, Xiong D K, Yi F Y. Iron-Based Metal-Organic Framework System as an Efficient Bifunctional Electrocatalyst for Oxygen Evolution and Hydrogen Evolution Reactions[J]. Inorg. Chem., 2020,59(9):6078-6086. doi: 10.1021/acs.inorgchem.0c00100
36. [36]
  Gan L, Fang J, Wang M R, Hu L T, Zhang K, Lai Y Q, Li J. Preparation of Double-Shell Co₉S₈/Fe₃O₄ Embedded in S/N Co-decorated Hollow Carbon nanoellipsoid Derived from Bi-metal Organic Frameworks for Oxygen Evolution Reaction[J]. J. Power Sources, 2018,391:59-66. doi: 10.1016/j.jpowsour.2018.04.082
37. [37]
  Dutta S, Indra A, Feng Y, Song T, Paik U. Self-Supported Nickel Iron Layered Double Hydroxide-Nickel Selenide Electrocatalyst for Superior Water Splitting Activity[J]. ACS Appl. Mater. Interfaces, 2017,9(39):33766-33774. doi: 10.1021/acsami.7b07984
38. [38]
  Zhang W D, Hu Q T, Wang L L, Gao J, Zhu H Y, Yan X D, Gu Z G. In-Situ Generated Ni-MOF/LDH Heterostructures with Abundant Phase Interfaces for Enhanced Oxygen Evolution Reaction[J]. Appl. Catal. B, 2021,286119906. doi: 10.1016/j.apcatb.2021.119906
1. [1]
  Endong YANG , Haoze TIAN , Ke ZHANG , Yongbing LOU . Efficient oxygen evolution reaction of CuCo₂O₄/NiFe-layered bimetallic hydroxide core-shell nanoflower sphere arrays. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 930-940. doi: 10.11862/CJIC.20230369
2. [2]
  Jiajie Li , Xiaocong Ma , Jufang Zheng , Qiang Wan , Xiaoshun Zhou , Yahao Wang . Recent Advances in In-Situ Raman Spectroscopy for Investigating Electrocatalytic Organic Reaction Mechanisms. University Chemistry, 2025, 40(4): 261-276. doi: 10.12461/PKU.DXHX202406117
3. [3]
  Xueting Cao , Shuangshuang Cha , Ming Gong . 电催化反应中的界面双电层：理论、表征与应用. Acta Physico-Chimica Sinica, 2025, 41(5): 100041-. doi: 10.1016/j.actphy.2024.100041
4. [4]
  Xin Han , Zhihao Cheng , Jinfeng Zhang , Jie Liu , Cheng Zhong , Wenbin Hu . Design of Amorphous High-Entropy FeCoCrMnBS (Oxy) Hydroxides for Boosting Oxygen Evolution Reaction. Acta Physico-Chimica Sinica, 2025, 41(4): 100033-. doi: 10.3866/PKU.WHXB202404023
5. [5]
  Qiangqiang SUN , Pengcheng ZHAO , Ruoyu WU , Baoyue CAO . Multistage microporous bifunctional catalyst constructed by P-doped nickel-based sulfide ultra-thin nanosheets for energy-efficient hydrogen production from water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1151-1161. doi: 10.11862/CJIC.20230454
6. [6]
  Yang WANG , Xiaoqin ZHENG , Yang LIU , Kai ZHANG , Jiahui KOU , Linbing SUN . Mn single-atom catalysts based on confined space: Fabrication and the electrocatalytic oxygen evolution reaction performance. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2175-2185. doi: 10.11862/CJIC.20240165
7. [7]
  Chuanming GUO , Kaiyang ZHANG , Yun WU , Rui YAO , Qiang ZHAO , Jinping LI , Guang LIU . Performance of MnO₂-0.39IrO_x composite oxides for water oxidation reaction in acidic media. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1135-1142. doi: 10.11862/CJIC.20230459
8. [8]
  Tongtong Zhao , Yan Wang , Shiyue Qin , Liang Xu , Zhenhua Li . New Experiment Development: Upgrading and Regeneration of Discarded PET Plastic through Electrocatalysis. University Chemistry, 2024, 39(3): 308-315. doi: 10.3866/PKU.DXHX202309003
9. [9]
  Jianchun Wang , Ruyu Xie . The Fantastical Dance of Miss Electron: Contra-Thermodynamic Electrocatalytic Reactions. University Chemistry, 2025, 40(4): 331-339. doi: 10.12461/PKU.DXHX202406082
10. [10]
  Ran HUO , Zhaohui ZHANG , Xi SU , Long CHEN . Research progress on multivariate two dimensional conjugated metal organic frameworks. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2063-2074. doi: 10.11862/CJIC.20240195
11. [11]
  Fangfang WANG , Jiaqi CHEN , Weiyin SUN . CuBi@Cu-MOF composite catalysts for electrocatalytic CO₂ reduction to HCOOH. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 97-104. doi: 10.11862/CJIC.20240350
12. [12]
  Jinyi Sun , Lin Ma , Yanjie Xi , Jing Wang . Preparation and Electrocatalytic Nitrogen Reduction Performance Study of Vanadium Nitride@Nitrogen-Doped Carbon Composite Nanomaterials: A Recommended Comprehensive Chemistry Experiment. University Chemistry, 2024, 39(4): 184-191. doi: 10.3866/PKU.DXHX202310094
13. [13]
  Xue Dong , Xiaofu Sun , Shuaiqiang Jia , Shitao Han , Dawei Zhou , Ting Yao , Min Wang , Minghui Fang , Haihong Wu , Buxing Han . 碳修饰的铜催化剂实现安培级电流电化学还原CO₂制C₂₊产物. Acta Physico-Chimica Sinica, 2025, 41(3): 2404012-. doi: 10.3866/PKU.WHXB202404012
14. [14]
  Xi Xu , Chaokai Zhu , Leiqing Cao , Zhuozhao Wu , Cao Guan . Experiential Education and 3D-Printed Alloys: Innovative Exploration and Student Development. University Chemistry, 2024, 39(2): 347-357. doi: 10.3866/PKU.DXHX202308039
15. [15]
  Linjie ZHU , Xufeng LIU . Electrocatalytic hydrogen evolution performance of tetra-iron complexes with bridging diphosphine ligands. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 321-328. doi: 10.11862/CJIC.20240207
16. [16]
  Bao Jia , Yunzhe Ke , Shiyue Sun , Dongxue Yu , Ying Liu , Shuaishuai Ding . Innovative Experimental Teaching for the Preparation and Modification of Conductive Organic Polymer Thin Films in Undergraduate Courses. University Chemistry, 2024, 39(10): 271-282. doi: 10.12461/PKU.DXHX202404121
17. [17]
  Jinfeng Chu , Yicheng Wang , Ji Qi , Yulin Liu , Yan Li , Lan Jin , Lei He , Yufei Song . Comprehensive Chemical Experiment Design: Convenient Preparation and Characterization of an Oxygen-Bridged Trinuclear Iron(III) Complex. University Chemistry, 2024, 39(7): 299-306. doi: 10.3866/PKU.DXHX202310105
18. [18]
  .
  CCS Chemistry 综述推荐│绿色氧化新思路：光/电催化助力有机物高效升级
  . CCS Chemistry, 2025, 7(10.31635/ccschem.024.202405369): -.
19. [19]
  Wenxiu Yang , Jinfeng Zhang , Quanlong Xu , Yun Yang , Lijie Zhang . Bimetallic AuCu Alloy Decorated Covalent Organic Frameworks for Efficient Photocatalytic Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(10): 2312014-. doi: 10.3866/PKU.WHXB202312014
20. [20]
  Kai CHEN , Fengshun WU , Shun XIAO , Jinbao ZHANG , Lihua ZHU . PtRu/nitrogen-doped carbon for electrocatalytic methanol oxidation and hydrogen evolution by water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1357-1367. doi: 10.11862/CJIC.20230350

Get Citation

PDF

XML

Metrics

PDF Downloads(8)
Abstract views(2012)
HTML views(234)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142