Biochar-supported PdCo catalyst facilitates hydrogenation of bio-based furfural under mild conditions: the function of biochar support

Abstract

Efficient biomass biochar-supported metal catalysts are essential for the conversion of biomass-derived chemicals. However, there is a lack of in-depth research on the function of biochar support. This research describes the direct loading of untreated sunflower stem pith (SP) with metal–organic frameworks (MOFs) as precursors, which were carbonized in a single step to produce Co-atom-evenly-doped biomass biochar support (Co/SPC), subsequently loaded with a low concentration of Pd to create a bimetallic catalyst (Pd-Co/SPC). The catalyst demonstrated remarkable efficacy in the hydrogenation of furfural (FAL) to tetrahydrofurfuryl alcohol (THFA), achieving a 99.9% yield within 1 h at 100 °C. This performance significantly surpassed that of Pd/SPC (28.1%) and the inactive Co/SPC, with the 99.9% yield sustained even at the milder temperature of 40 °C. The excellent catalytic performance of the Pd-Co/SPC catalyst was attributed to three main aspects. First, controlled experiments and characterization results demonstrated that the acidic and basic nature of the sunflower pith-derived biochar support promoted the activation of FAL. Second, the interaction between the biochar support and the metal not only inhibited the agglomeration of metal particles but also augmented the electron density of the PdCo metal and facilitated the activation of H₂. Finally, the synergistic interaction between the highly dispersed Pd and Co facilitated the activation of H₂ and stabilized the intermediate furfuryl alcohol (FOL). Furthermore, this superior metal-support interaction contributed to the increased stability of the catalyst. This work presents a novel approach for the high-value utilization of biochar and highly efficient catalysis of biomass conversion.

Keywords

Sunflower stem pith carbon / PdCo catalyst / Catalyze / Furfural / Hydrogenation

References

[1] Ahmad YH, Mohamed AT, Kumar A, Al-Qaradawi SY. Solution combustion synthesis of Ni/La₂O₃ for dry reforming of methane: tuning the basicity via alkali and alkaline earth metal oxide promoters. RSC Adv, 2021, 11: 33734-33743

[2] Akram M, Bhutto SUA, Aftab S, Wang F, Xu X, Xia M. Ruthenium based with carbon supported catalysts for the catalytic transfer hydrogenation of furfural: a review. Nano Energy, 2023

[3] Albilali R, Douthwaite M, He Q, Taylor SH. The selective hydrogenation of furfural over supported palladium nanoparticle catalysts prepared by sol-immobilisation: effect of catalyst support and reaction conditions. Catal Sci Technol, 2018, 8: 252-267

[4] Al-Fatesh AS, Naeem MA, Fakeeha AH, Abasaeed AE. Role of La₂O₃ as promoter and support in Ni/γ-Al₂O₃ catalysts for dry reforming of methane. Chin J Chem Eng, 2014, 22: 28-37

[5] An Z, Li J. Recent advances in the catalytic transfer hydrogenation of furfural to furfuryl alcohol over heterogeneous catalysts. Green Chem, 2022, 24: 1780-1808

[6] Bartoli M, Giorcelli M, Tagliaferro A. A comprehensive overview on biochar-based materials for catalytic applications. Catalysts, 2023

[7] Chada RR, Enumula SS, Koppadi KS, Babu Gurram VR, Rao Kamaraju SR, Burri DR. Pd/SBA-15 catalysts for hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol. ChemSelect, 2018, 3: 9946-9952

[8] Chakarova K, Mihaylov M, Hadjiivanov K. FTIR spectroscopic study of CO adsorption on Pt–H–ZSM-5. Microporous Mesoporous Mater, 2005, 81: 305-312

[9] Chen X, Sun W, Xiao N, Yan Y, Liu S. Erratum to “Experimental study for liquid phase selective hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol on supported Ni catalysts”. Chem Eng J, 2008

[10] Chen M, Zhao G, Shao L-L, Yuan Z-Y, Jing Q-S, Huang K-J, Huang Z-Y, Zhao X-H, Zou G-D. Controlled synthesis of nickel encapsulated into nitrogen-doped carbon nanotubes with covalent bonded interfaces: the structural and electronic modulation strategy for an efficient electrocatalyst in dye-sensitized solar cells. Chem Mater, 2017, 29: 9680-9694

[11] Chin SY, Williams CT, Amiridis MD. FTIR studies of CO adsorption on Al₂O₃- and SiO₂-supported Ru catalysts. J Phys Chem B, 2006

[12] Cho EH, Park Y-K, Park KY, Song D, Koo KY, Jung U, Yoon WR, Ko CH. Simultaneous impregnation of Ni and an additive via one-step melt-infiltration: effect of alkaline-earth metal (Ca, Mg, Sr, and Ba) addition on Ni/γ-Al₂O₃ for CO₂ methanation. Chem Eng J, 2022

[13] Dou M, Qiao Y, Hu X, Miao H, Zhou L, Li X, Hou X, Wang Y, Tang M. Gradient porous biochar materials with high specific surface area as supports for Pd/C catalysts for efficient maleic acid hydrogenation. Mol Catal, 2023

[14] Furukawa S, Komatsu T, Shimizu K-I. Catalyst design concept based on a variety of alloy materials: a personal account and relevant studies. J Mater Chem A, 2020, 8: 15620-15645

[15] Gao Y, Zhao H, Liang J, Liu C, Yuan H, Zheng Y, Li H, Wang F, Dong Z. Highly selective catalytic hydrogenation of furfural and acetophenone on S-doped mesoporous carbon sphere-supported Pd nanocluster catalyst. Chem Eng J, 2025

[16] Gong W, Chen C, Zhang H, Zhang Y, Zhang Y, Wang G, Zhao H. Highly selective liquid-phase hydrogenation of furfural over N-doped carbon supported metallic nickel catalyst under mild conditions. Mol Catal, 2017, 429: 51-59

[17] Gowda AS, Parkin S, Ladipo FT. Hydrogenation and hydrogenolysis of furfural and furfuryl alcohol catalyzed by ruthenium(II) bis(diimine) complexes. Appl Organomet Chem, 2012, 26: 86-93

[18] He Y, Guo H, Hwang S, Yang X, He Z, Braaten J, Karakalos S, Shan W, Wang M, Zhou H, Feng Z, More KL, Wang G, Su D, Cullen DA, Fei L, Litster S, Wu G. Single cobalt sites dispersed in hierarchically porous nanofiber networks for durable and high-power PGM-free cathodes in fuel cells. Adv Mater, 2020

[19] Henao W, Cazaña F, Tarifa P, Romeo E, Latorre N, Sebastian V, Delgado JJ, Monzón A. Selective synthesis of carbon nanotubes by catalytic decomposition of methane using Co-Cu/cellulose derived carbon catalysts: a comprehensive kinetic study. Chem Eng J, 2021

[20] Kamble PA, Vinod CP, Rathod VK, Kantam ML. Hydrogenation of furfural to tetrahydrofurfuryl alcohol over nickel-supported on organoclay catalyst. Appl Catal A Gen, 2024

[21] Kim G, Kim YE, Jae J, Lee MS. Effect of physicochemical properties of carbons on the performance of bead-type Pd/C catalysts for furfural hydrogenation. Mol Catal, 2024

[22] Lan F, Aarons J, Shu Y, Zhou X, Jiao H, Wang H, Guan Q, Li W. Anchoring strategy for highly active copper nanoclusters in hydrogenation of renewable biomass-derived compounds. Appl Catal B Environ, 2021

[23] Li C, Xu G, Liu X, Zhang Y, Fu Y. Hydrogenation of biomass-derived furfural to tetrahydrofurfuryl alcohol over hydroxyapatite-supported Pd catalyst under mild conditions. Ind Eng Chem Res, 2017, 56: 8843-8849

[24] Li Z, Wang M, Jin C, Kang J, Liu J, Yang H, Zhang Y, Pu Q, Zhao Y, You M, Wu Z. Synthesis of novel Co₃O₄ hierarchical porous nanosheets via corn stem and MOF-Co templates for efficient oxytetracycline degradation by peroxymonosulfate activation. Chem Eng J, 2020

[25] Li Y, Wu Y, Delbari SA, Kim A, Namini AS, Le QV, Xia C, Luque R, Jang HW, Shokouhimehr M, Varma RS. Functional carbon-supported nanocatalysts for biomass conversion. Mol Catal, 2023

[26] Long Z, Sun L, Zhu W, Chen G, Wang X, Sun W. P-doped carbons derived from cellulose as highly efficient metal-free catalysts for aerobic oxidation of benzyl alcohol in water under an air atmosphere. Chem Commun, 2018, 54: 8991-8994

[27] Lukashuk L, Yigit N, Rameshan R, Kolar E, Teschner D, Hävecker M, Knop-Gericke A, Schlögl R, Föttinger K, Rupprechter G. Operando insights into CO oxidation on cobalt oxide catalysts by NAP-XPS, FTIR, and XRD. ACS Catal, 2018, 8: 8630-8641

[28] Ma Q, Liu C, Zhu Y, Zheng Y, Wu Y, Gao W, Wang F, Dong Z. Small-molecule-assisted formation of Pd nanoclusters on N-doped mesoporous carbon for improved semi-hydrogenation of alkynols. Chem Eng J, 2025

[29] Matsagar BM, Yang R-X, Dutta S, Ok YS, Wu KCW. Recent progress in the development of biomass-derived nitrogen-doped porous carbon. J Mater Chem A, 2021, 9: 3703-3728

[30] Medina Ruiz ME, Maderuelo-Solera R, Jiménez-Gómez CP, Moreno-Tost R, Malpartida I, García-Sancho C, Cecilia JA, Len C, Mérida-Robles JM, Maireles-Torres P. Supported palladium catalysts for the selective hydrogenation of furfural with polymethylhydrosiloxane. ACS Sustain Chem Eng, 2024, 12: 14910-14920

[31] Mohandessi M, Kiani MR, Yousefi S, Rahimpour MR. Tuning the basicity of the Ni@MCM-41 catalyst via alkaline earth metal oxide promoters for CO₂ reforming of CH₄. React Chem Eng, 2023, 8: 1349-1361

[32] Pirmoradi M, Janulaitis N, Gulotty RJ, Kastner JR. Bi-metal-supported activated carbon monolith catalysts for selective hydrogenation of furfural. Ind Eng Chem Res, 2020, 59: 17748-17761

[33] Pu S, Zhai Z, Yang C, Dao Z, Yan W, Zhuang C, Min C, Zhao J, Wang Y. Deep eutectic solvent-derived carbon-based FeNi bimetallic catalysts for selective hydrogenation of furfural. Chem Eng J, 2025

[34] Rao TU, Suchada S, Choi C, Machida H, Huo Z, Norinaga K. Selective hydrogenation of furfural to tetrahydrofurfuryl alcohol in 2-butanol over an equimolar Ni-Cu-Al catalyst prepared by the co-precipitation method. Energy Convers Manag, 2022

[35] Sheng Y, Tian F, Wang X, Jiang N, Zhang X, Chen X, Liang C, Wang A. Carbon-encapsulated Ni catalysts derived from citrate complexes for highly efficient hydrogenation of furfural to tetrahydrofurfuryl alcohol. Energy, 2024

[36] Shi Y, Zhu J, Yuan G, Liu G, Wang Q, Sun W, Zhao B, Wang L, Zhang H. Activation of persulfate by EDTA-2K-derived nitrogen-doped porous carbons for organic contaminant removal: radical and non-radical pathways. Chem Eng J, 2020

[37] Singha RK, Yadav A, Agrawal A, Shukla A, Adak S, Sasaki T, Bal R. Synthesis of highly coke resistant Ni nanoparticles supported MgO/ZnO catalyst for reforming of methane with carbon dioxide. Appl Catal B Environ, 2016, 191: 165-178

[38] Sun Q, Wang N, Bing Q, Si R, Liu J, Bai R, Zhang P, Jia M, Yu J. Subnanometric hybrid Pd-M(OH)2, M = Ni Co, clusters in zeolites as highly efficient nanocatalysts for hydrogen generation. Chem, 2017, 3: 477-493

[39] Tan Y, Yu R, Cheng J, Zhao H, Du Y, Yao H, Li J. Sinter-resistant platinum nanocatalysts immobilized by biochar for alkane hydroisomerization. Catal Sci Technol, 2021, 11: 7740-7750

[40] Taylor MJ, Durndell LJ, Isaacs MA, Parlett CMA, Wilson K, Lee AF, Kyriakou G. Highly selective hydrogenation of furfural over supported Pt nanoparticles under mild conditions. Appl Catal B Environ, 2016, 180: 580-585

[41] Thompson ST, Lamb HH. Palladium-Rhenium catalysts for selective hydrogenation of furfural: evidence for an optimum surface composition. ACS Catal, 2016, 6: 7438-7447

[42] Villaverde MM, Bertero NM, Garetto TF, Marchi AJ. Selective liquid-phase hydrogenation of furfural to furfuryl alcohol over Cu-based catalysts. Catal Today, 2013, 213: 87-92

[43] Wang L, Ren L, Wang X, Feng X, Zhou J, Wang B. Multivariate MOF-templated pomegranate-like Ni/C as efficient bifunctional electrocatalyst for hydrogen evolution and urea oxidation. ACS Appl Mater Interfaces, 2018, 10: 4750-4756

[44] Wang D, Zhao P, Yang J, Xu G, Yang H, Shi Z, Hu Q, Dong B, Guo Z. Photocatalytic degradation of organic dye and phytohormone by a Cu(II) complex powder catalyst with added H2O2. Colloids Surf A Physicochem Eng Asp, 2020

[45] Wang Y, Gao T, Lu Y, Wang Y, Cao Q, Fang W. Efficient hydrogenation of furfural to furfuryl alcohol by magnetically recoverable RuCo bimetallic catalyst. Green Energy Environ, 2022, 7: 275-287

[46] Wang Z, Yang Y, Wang X, Lu Z, Guo C, Shi Y, Tan H, Shen L, Cao S, Yan C. A three-dimensional ordered honeycomb nanostructure anchored with Pt–N active sites via self-assembly of a block copolymer: an efficient electrocatalyst towards the oxygen reduction reaction in fuel cells. J Mater Chem A, 2022, 10: 12141-12149

[47] Wang Y, Chen M, Zhang K, Wu H, Wang J, Cheng Y, Liu Y, Wei Z. CoNi alloy nanoparticles confined in N-doped porous carbon as an efficient and versatile catalyst for reductive amination of levulinic acid/esters to N-substituted pyrrolidones. ACS Catal, 2023, 13: 12601-12616

[48] Wei YS, Zou L, Wang HF, Wang Y, Xu Q. Micro/nano-scaled metal-organic frameworks and their derivatives for energy applications. Adv Energy Mater, 2021

[49] Xia Z, Niu L, An Y, Bian G, Li T, Bai G. Ni–Al/CoOx-catalyzed hydrodeoxygenation of 5-hydroxymethylfurfural into 2,5-dimethylfuran at low temperatures without external hydrogen. Green Chem, 2021, 23: 7763-7772

[50] Xie X, Shi J, Pu Y, Wang Z, Zhang L-L, Wang J-X, Wang D. Cellulose derived nitrogen and phosphorus co-doped carbon-based catalysts for catalytic reduction of p-nitrophenol. J Colloid Interface Sci, 2020, 571: 100-108

[51] Xu Y, Liu S, Wang M, Zhang J, Ding H, Song Y, Zhu Y, Pan Q, Zhao C, Deng H. Thiourea-assisted one-step fabrication of a novel nitrogen and sulfur co-doped biochar from nanocellulose as metal-free catalyst for efficient activation of peroxymonosulfate. J Hazard Mater, 2021

[52] Yan K, Chen A. Efficient hydrogenation of biomass-derived furfural and levulinic acid on the facilely synthesized noble-metal-free Cu–Cr catalyst. Energy, 2013, 58: 357-363

[53] Yan J, Liu T, Liu X, Yan Y, Huang Y. Metal-organic framework-based materials for flexible supercapacitor application. Coord Chem Rev, 2022

[54] You J, Zhang C, Wu Z, Ao Z, Sun W, Xiong Z, Su S, Yao G, Lai B. N-doped graphite encapsulated metal nanoparticles catalyst for removal of Bisphenol A via activation of peroxymonosulfate: a singlet oxygen-dominated oxidation process. Chem Eng J, 2021

[55] Zhang L, Tian L, Sun R, Liu C, Kou Q, Zuo H. Transformation of corncob into furfural by a bifunctional solid acid catalyst. Bioresour Technol, 2019, 276: 60-64

[56] Zhang S, Xia W, Yang Q, Valentino Kaneti Y, Xu X, Alshehri SM, Ahamad T, Hossain MSA, Na J, Tang J, Yamauchi Y. Core-shell motif construction: highly graphitic nitrogen-doped porous carbon electrocatalysts using MOF-derived carbon@COF heterostructures as sacrificial templates. Chem Eng J, 2020

[57] Zhang X, Liu J, Li T, Li G, Zhao Y, Wang Y, Lv Y, Zhang G. Co-based defect-rich nanoarchitectonics with biomass carbon materials catalysts for CH₄–CO₂ reforming. Mol Catal, 2023

[58] Zhang J, Liu Y, Jia Z, Yu S, Liu S, Li L, Wu Q, Yu H, Liu Y, Jiang X, Liu Y, Xu C. Selective hydrogenation of furfural to furfuryl alcohol over copper-cobalt bimetallic catalyst. Chem Eng J, 2024

[59] Zheng G, Huang Z, Liu Z. Cooperative utilization of beet pulp and industrial waste fly ash to produce N/P/O self-co-doped hierarchically porous carbons for high-performance supercapacitors. J Power Sour, 2021

[60] Zhong Y, Wu Z, Liu X, Li L. Highly active rGO/Ca-MOF loaded Pd-M (M = Fe, Sb, Pb, Sn, Ag) composite catalysts towards ethylene glycol electrooxidation. J Electroanal Chem, 2022

[61] Zhou Y, Li Z, Liu Y, Huo J, Chen C, Li Q, Niu S, Wang S. Regulating hydrogenation chemoselectivity of α,β-unsaturated aldehydes by combination of transfer and catalytic hydrogenation. Chemsuschem, 2020, 13: 1746-1750

[62] Zhou Y, Abazari R, Chen J, Tahir M, Kumar A, Ikreedeegh RR, Rani E, Singh H, Kirillov AM. Bimetallic metal–organic frameworks and MOF-derived composites: recent progress on electro- and photoelectrocatalytic applications. Coord Chem Rev, 2022

Funding

National Natural Science Foundation of China(32360430)

Science and Technology Planning Project of Yunnan Province(202401BD070001-030)

Young and Middle-aged Academic and Technical Leaders Project in Yunnan Province(202205AC160052)

The Young and Middle-aged Technology Innovation Leading Talents, the Team Projects of Science and Technology Development Plan of Jilin Province(20230508041RC)

RIGHTS & PERMISSIONS

The Author(s)