Citation: Xinlong XU, Chunxue JING, Yuzhen CHEN. Bimetallic MOF-74 and derivatives: Fabrication and efficient electrocatalytic biomass conversion[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(8): 1545-1554. doi: 10.11862/CJIC.20250046 shu

Bimetallic MOF-74 and derivatives: Fabrication and efficient electrocatalytic biomass conversion

College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao, Shandong 266042, China

Corresponding author: Yuzhen CHEN, yzchen@qust.edu.cn
Received Date: 15 March 2025
Revised Date: 8 May 2025

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This work focuses on fabricating multifunctional electrode materials and reaction systems for the highly efficient 5-hydroxymethylfurfural (HMF) oxidation under mild conditions. Bimetallic metal-organic framework materials (BMOF) and their derivatives were synthesized for the electrocatalytic oxidation of HMF at low voltage. Bimetallic CoNi-MOF-74 was synthesized using the solvothermal method. Two methods were used to transform the MOF material into electrode materials. Firstly, the CoNi alloy particles stabilized by porous carbon matrix (denoted asCoNi@C) were obtained by pyrolysis of CoNi-MOF-74. Secondly, the CoNi(OH)₂ was in situ and obtained through the hydrolysis of CoNi-MOF-74 under an alkaline electrolyte during electrocatalysis. Interestingly, the optimal Co₁Ni₃@C derived from Co₁Ni₃-MOF-74 via pyrolysis at 800 ℃ exhibited excellent catalytic activity and high 2, 5- furandicarboxylic acid (FDCA) selectivity (87.26%) for HMF electrooxidation at low potential. The Co_0.5Ni_0.5(OH)₂ generated in situ during electrolysis of Co₁Ni₁-MOF-74 displayed high selectivity (88.59%) for the intermediate product of 5-(hydroxymethyl) furano-2-carboxylic acid (HMFCA). The superior performance is mainly attributed to the pore structure of the catalytic materials, the synergistic effect between Co and Ni, and the good electrical conductivity of graphitic carbon.
- metal-organic framework material,
- non-noble metal,
- electrocatalysis,
- biomass conversion,
- 5-hydroxymethylfurfural oxidation
1. [1]
  HOFMANN M A, SHAHID A T, GARRIDO M, FERREIRA M J, CORREIA J R, BORDADO J C. Biobased thermosetting polyester resin for high-performance applications[J]. ACS Sustain. Chem. Eng., 2022, 10(11): 3442-3454
2. [2]
  LI N, ZONG M H. (Chemo)Biocatalytic upgrading of biobased furanic platforms to chemicals, fuels, and materials: A comprehensive review[J]. ACS Catal., 2022, 12(16): 10080-10114
3. [3]
  SCHADE O R, DANNECKER P K, KALZ K F, STEINBACH D, MEIER M A R, GRUNWALDT J D. Direct catalytic route to biomass-derived 2, 5-furandicarboxylic acid and its use as monomer in a multicomponent polymerization[J]. ACS Omega, 2019, 4(16): 16972-16979
4. [4]
  EERHART A J J E, FAAIJ A P C, PATEL M K. Replacing fossil based PET with biobased PEF; process analysis, energy and GHG balance[J]. Energy Environ. Sci., 2012, 5(4): 6407-6422
5. [5]
  SAJID M, ZHAO X B, LIU D H. Production of 2, 5-furandicarboxylic acid (FDCA) from 5-hydroxymethylfurfural (HMF): Recent progress focusing on the chemical-catalytic routes[J]. Green Chem., 2018, 20(24): 5427-5453
6. [6]
  LU Y, DONG C L, HUANG Y C, ZOU Y, LIU Z, LIU Y, LI Y, HE N, SHI J, WANG S. Identifying the geometric site dependence of spinel oxides for the electrooxidation of 5-hydroxymethylfurfural[J]. Angew. Chem. ‒Int. Edit., 2020, 59(43): 19215-19221
7. [7]
  MITTAL A, PILATH H M, JOHNSON D K. Direct conversion of biomass carbohydrates to platform chemicals: 5-hydroxymethylfurfural (HMF) and furfural[J]. Energy Fuels, 2020, 34(3): 3284-3293
8. [8]
  ZHOU H, SU Z H, KONG X G, DUAN H G. Recent progress in electrochemical catalytic conversion of biomass platform molecules into high-value added fuels and chemicals[J]. Chem. J. Chinese Universities, 2020, 41(7): 1449-1460
9. [9]
  LIU G, SUN F Z, FU S Q, LI Y J, LI Z, HUANG X Q. Research progress of polyoxometalates in electrocatalytic chemical conversion[J]. Journal of Liaocheng University (Natural Science Edition), 2024, 37(4): 89-102
10. [10]
  ZHOU B, LI Y Y, ZOU Y Q, CHEN W, ZHOU W, SONG M L, WU Y J, LU Y X, LIU J L, WANG Y Y, WANG S Y. Platinum modulates redox properties and 5-hydroxymethylfurfural adsorption kinetics of Ni(OH)₂ for biomass upgrading[J]. Angew. Chem. ‒Int. Edit., 2021, 60: 22908-22914
11. [11]
  WU Q J, SI D H, YE S, DONG Y L, CAO R, HUANG Y B. Photocoupled electroreduction of CO₂ over photosensitizer-decorated covalent organic frameworks[J]. J. Am. Chem. Soc., 2023, 145(36): 19856-19865
12. [12]
  YOU B, LIU X, JIANG N, SUN Y J. A general strategy for decoupled hydrogen production from water splitting by integrating oxidative biomass valorization[J]. J. Am. Chem. Soc., 2016, 138(41): 13639-13646
13. [13]
  ZHANG N N, ZOU Y Q, TAO L, CHEN W, ZHOU L, LIU Z J, ZHOU B, HUANG G, LIN H Z, WANG S Y. Electrochemical oxidation of 5-hydroxymethylfurfural on nickel nitride/carbon nanosheets: Identified pathway by in situ sum frequency generation vibrational spectroscopy[J]. Angew. Chem. ‒Int. Edit., 2019, 58(44): 15895-15903
14. [14]
  OU W, YE X, ZHOU Y. Recent advances in Ni(oxy) hydroxides and Ni sulfides catalysts for oxygen evolution reactions[J]. Coord. Chem. Rev., 2023, 493: 215274
15. [15]
  ZHANG P L, SHENG X, CHEN X Y, FANG Z Y, JIANG J, WANG M, LI F S, FAN L Z, REN Y S, ZHANG B B, TIMMER B J J, AHLQUIST M S G, SUN L C. Paired electrocatalytic oxygenation and hydrogenation of organic substrates with water as the oxygen and hydrogen source[J]. Angew. Chem. ‒Int. Edit., 2019, 58(27): 9155-9159
16. [16]
  KANG Q, LAI D, TANG W, LU Q, GAO F. Intrinsic activity modulation and structural design of NiFe alloy catalysts for an efficient oxygen evolution reaction[J]. Chem. Sci., 2021, 12: 3818-3835
17. [17]
  ZHOU W J, JIA J, LU J, YANG L J, HOU D M, LI G Q, CHEN S W. Recent developments of carbon-based electrocatalysts for hydrogen evolution reaction[J]. Nano Energy, 2016, 28: 29-43
18. [18]
  ISLAMOGLU T, GOSWAMI S, Li Z, HOWARTH A J, FARHA O K, HUPP J T. Postsynthetic tuning of metal-organic frameworks for targeted applications[J]. Accounts Chem. Res., 2017, 50(4): 805-813
19. [19]
  LIAO P Q, HUANG N Y, ZHANG W X, ZHANG J P, CHEN X M. Controlling guest conformation for efficient purification of butadiene[J]. Science, 2017, 356(6343): 1193-1196
20. [20]
  YAGHI O M, RONG Z C. Decoding complex order in reticular frameworks[J]. Science, 2023, 379(6630): 330-331
21. [21]
  CHEN Y Z, WANG C, WUN Z Y, XIONG Y, XU Q, YU S H, JIANG H L. From bimetallic metal-organic framework to porous carbon: High surface area and multicomponent active dopants for excellent electrocatalysis[J]. Adv. Mater., 2015, 27(34): 5010-5016
22. [22]
  ZHAO M T, YUAN K, WANG Y, LI G D, GUO J, GU L, HU W P, ZHAO H J, TANG Z Y. Metal-organic frameworks as selectivity regulators for hydrogenation reactions[J]. Nature, 2016, 539: 76-80
23. [23]
  JIANG H L, LIU B, LAN Y Q, KURATANI K, AKITA T, SHIOYAMA H, ZONG F Q, XU Q. From metal-organic framework to nanoporous carbon: Toward a very high surface area and hydrogen uptake[J]. J. Am. Chem. Soc., 2011, 133(31): 11854-11857
24. [24]
  XING J L, GUO K L, ZOU Z H, CAI M M, DU J, XU C L. In situ growth of well-ordered NiFe-MOF-74 on Ni foam by Fe²⁺ induction as an efficient and stable electrocatalyst for water oxidation[J]. Chem. Commun., 2018, 54(51): 7046-7049
25. [25]
  JAGADEESH R V, MURUGESAN K, ALSHAMMARI A S, NEUMANN H, POHL M M, RADNIK J, BELLER M. MOF-derived cobalt nanoparticles catalyze a general synthesis of amines[J]. Science, 2017, 358(6361): 326-332
26. [26]
  CHEN Y Z, ZHANG R, JIAO L, JIANG H L. Metal-organic framework-derived porous materials for catalysis[J]. Coord. Chem. Rev., 2018, 362: 1-23
27. [27]
  YIN H Q, ZHANG Z M, LU T B. Ordered integration and heterogenization of catalysts and photosensitizers in metal-/covalent-organic frameworks for boosting CO₂ photoreduction[J]. Accounts Chem. Res., 2023, 56(19): 2676-2687
28. [28]
  WANG F. Solvent-directed syntheses of two hydrogen-bonded metal-organic frameworks[J]. Journal of Liaocheng University (Natural Science Edition), 2024, 37(5): 102-110
29. [29]
  WANG N N, CHEN Y Z. CoNi-MOF-74/NF Derived CoNi@C/NF hybrid for efficient electrosynthesis of organics[J]. Acta Chim. Sinica, 2024, 82(6): 621-628
30. [30]
  LI Z H, LIU H, SONG L Y, HUANG T H. Synthesis of dual-metal functionalized MOF-74 and its adsorption properties[J]. Chinese J. Inorg. Chem., 2017, 33(2): 237-242
31. [31]
  ZHANG H B, XU B, MEI H, MEI Y J, ZHANG S Y, YANG Z D, XIAO Z Y, KANG W P, SUN D F. "HOT" alkaline hydrolysis of amorphous MOF microspheres to produce ultrastable bimetal hydroxide electrode with boosted cycling stability[J]. Small, 2019, 15(49): 1904663
32. [32]
  REN G X, LIU B C, LIU L, HU M H, ZHU J P, XU X, JING P, WU J F, ZHANG J. Regulating the electronic structure of Ni sites in Ni(OH)₂ by Ce doping and Cu(OH)₂ coupling to boost 5-hydroxymethylfurfural oxidation performance[J]. Inorg. Chem., 2023, 62(31): 12534-12547
33. [33]
  LI H M, HUANG X Y, LV Y, ZHANG J L, LI W. Highly efficient electrooxidation of 5-hydroxymethylfurfural (HMF) by Cu regulated Co carbonate hydroxides boosting hydrogen evolution reaction[J]. Int. J. Hydrog. Energy, 2023, 48(97): 38279-38295
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