Ni nanoparticles with high thermal stability for methane dry reforming

Meng Han , Dan Guo , Xuening Zhang , Yitong Yao , Haozhe Zhang , Yifei Lu , Zelong Fu , Jing Lv , Yong Wang , Joe Yeang Cheah , Shengping Wang , Xinbin Ma

Front. Chem. Sci. Eng. ›› 2025, Vol. 19 ›› Issue (8) : 70

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Front. Chem. Sci. Eng. ›› 2025, Vol. 19 ›› Issue (8) : 70 DOI: 10.1007/s11705-025-2580-z
RESEARCH ARTICLE

Ni nanoparticles with high thermal stability for methane dry reforming

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Abstract

The upgrading of underutilized methane in shale gas with anthropogenic CO2 can produce the value-added syngas via dry reforming. Nickel-based catalysts, due to their efficiency and cost-effectiveness, have received widespread attention. However, Ni-catalyzed dry reforming of methane is usually subjected to sintering or coking-induced instability. To address these issues, a series of Al2O3-supported nickel nanoparticle catalysts with uniform sizes are synthesized by varying the calcination temperatures and applied in methane dry reforming (DRM). Ni/Al2O3-700 °C catalyst behaves better catalytic performance compared to the other catalysts, which can be attributed to its higher metal dispersion and stronger metal-support interaction. In addition, the abundant moderate-strength basic sites and optimal AlIV/AlVI ratio can promote the adsorption and activation of CO2 and suppress the deep cracking of CH4 for Ni/Al2O3-700 °C catalyst, respectively, causing the enhancement of anti-coking performance. Furthermore, combining CH4-temperature programmed surface reaction and in situ Fourier transform infrared spectroscopy demonstrates that the presence of CO2 can promote the activation of CH4 for Ni/Al2O3-700 °C catalyst, which is rate-determining step for DRM system. These findings provide valuable theoretical guidance for the rational design of Ni-based catalysts with enhanced catalytic performance.

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Keywords

dry reforming of methane / nickel-based catalysts / calcination temperature / metal-support interaction

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Meng Han, Dan Guo, Xuening Zhang, Yitong Yao, Haozhe Zhang, Yifei Lu, Zelong Fu, Jing Lv, Yong Wang, Joe Yeang Cheah, Shengping Wang, Xinbin Ma. Ni nanoparticles with high thermal stability for methane dry reforming. Front. Chem. Sci. Eng., 2025, 19(8): 70 DOI:10.1007/s11705-025-2580-z

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References

[1]

Shi Y , Tian X Y , Deng Z Y , Shi W , Fan W , Wang F . Review and outlook of confined Ni catalysts for the dry reforming of methane reaction. Energy & Fuels, 2024, 38(3): 1633–1656

[2]

Deng J , Bu K , Shen Y , Zhang X , Zhang J , Faungnawakij K , Zhang D . Cooperatively enhanced coking resistance via boron nitride coating over Ni-based catalysts for dry reforming of methane. Applied Catalysis B: Environmental, 2022, 302: 120859

[3]

Solomon S , Plattner G K , Knutti R , Friedlingstein P . Irreversible climate change due to carbon dioxide emissions. Proceedings of the National Academy of Sciences of the United States of America, 2009, 106(6): 1704–1709

[4]

Elvidge C D , Bazilian M D , Zhizhin M , Ghosh T , Baugh K , Hsu F C . The potential role of natural gas flaring in meeting greenhouse gas mitigation targets. Energy Strategy Reviews, 2018, 20: 156–162

[5]

Yentekakis I V , Panagiotopoulou P , Artemakis G . A review of recent efforts to promote dry reforming of methane (DRM) to syngas production via bimetallic catalyst formulations. Applied Catalysis B: Environmental, 2021, 296: 120210

[6]

Landi G , Sorbino G , Migliardini F , Ruoppolo G , Di Benedetto A . Enhanced activity of bimetallic Fe-Cu catalysts supported on ceria toward water gas shift reaction: synergistic effect. Frontiers of Chemical Science and Engineering, 2023, 17(12): 1962–1972

[7]

Li H Y , Gao J M , Shan J J , Du Q , Zhang Y , Guo X , Wu S , Wang Z . Boosting the direct conversion of NH4HCO3 electrolyte to syngas on Ag/Zn zeolitic imidazolate framework derived nitrogen-carbon skeleton. Frontiers of Chemical Science and Engineering, 2023, 17(9): 1196–1207

[8]

Zhang X , Deng J , Pupucevski M , Impeng S , Yang B , Chen G , Kuboon S , Zhong Q , Faungnawakij K , Zheng L . . High-performance binary Mo-Ni catalysts for efficient carbon removal during carbon dioxide reforming of methane. ACS Catalysis, 2021, 11(19): 12087–12095

[9]

Gharibi M , Zangeneh F T , Yaripour F , Sahebdelfar S . Nanocatalysts for conversion of natural gas to liquid fuels and petrochemical feedstocks. Applied Catalysis A: General, 2012, 443: 8–26

[10]

Chan Y H , Yiin C L , Huang M M , Lock S S M , Chin B L F , Wee J S , Foong S Y , Lam S S . Advances in bi-reforming of methane: syngas production for low-carbon energy solutions. Chemical Engineering Journal, 2025, 505: 159660

[11]

Wang Y , Yang N , Wang Z , Feng D . Developing indium-oxide based catalysts for efficient hydrogenation of carbon dioxide to methanol: a mini-review. Frontiers of Chemical Science and Engineering, 2025, 19(3): 1–22

[12]

Pereira V G F , Serrano-Lotina A , Portela R , Bañares M , Rodrigues C , Toniolo F . Ni/Al2O3 promoted by CeO2, CeO2-La2O3, and CeO2-ZrO2 supported on cordierite monoliths for methane steam reforming. Catalysis Today, 2025, 445: 115107

[13]

Shan J J , Li M W , Allard L F , Lee S , Flytzani-Stephanopoulos M . Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts. Nature, 2017, 551(7682): 605–608

[14]

Hou Z Y , Chen P , Fang H L , Zheng X , Yashima T . Production of synthesis gas via methane reforming with CO2 on noble metals and small amount of noble-(Rh-) promoted Ni catalysts. International Journal of Hydrogen Energy, 2006, 31(5): 555–561

[15]

Gamal A , Eid K , Abdullah A M . Engineering of Pt-based nanostructures for efficient dry (CO2) reforming: strategy and mechanism for rich-hydrogen production. International Journal of Hydrogen Energy, 2022, 47(9): 5901–5928

[16]

Sharifianjazi F , Esmaeilkhanian A , Bazli L , Eskandarinezhad S , Khaksar S , Shafiee P , Yusuf M , Abdullah B , Salahshour P , Sadeghi F . A review on recent advances in dry reforming of methane over Ni- and Co-based nanocatalysts. International Journal of Hydrogen Energy, 2022, 47(100): 42213–42233

[17]

Huang L A , Li D Y , Tian D , Jiang L , Li Z , Wang H , Li K . Optimization of Ni-based catalysts for dry reforming of methanevia alloy design: a review. Energy & Fuels, 2022, 36(10): 5102–5151

[18]

Deng J , Gao M , Hasegawa J Y , Zhang X , Wang A , Chen A , Zhang D . Unravelling the anomalous coking resistance over boron nitride-supported Ni catalysts for dry reforming of methane. CCS Chemistry, 2022, 5(9): 2111–2124

[19]

Xu L L , Zhao H , Song H L , Chou L . Ordered mesoporous alumina supported nickel based catalysts for carbon dioxide reforming of methane. International Journal of Hydrogen Energy, 2012, 37(9): 7497–7511

[20]

Kim J H , Suh D J , Park T J , Kim K L . Effect of metal particle size on coking during CO2 reforming of CH4 over Ni-alumina aerogel catalysts. Applied Catalysis A: General, 2000, 197(2): 191–200

[21]

Wang Z T , Hu X , Dong D H , Parkinson G , Li C Z . Effects of calcination temperature of electrospun fibrous Ni/Al2O3 catalysts on the dry reforming of methane. Fuel Processing Technology, 2017, 155: 246–251

[22]

Schwach P , Pan X L , Bao X H . Direct conversion of methane to value-added chemicals over heterogeneous catalysts: challenges and prospects. Chemical Reviews, 2017, 117(13): 8497–8520

[23]

He Y X , Yin L , Yuan N N , Zhang G . Adsorption and activation, active site and reaction pathway of photocatalytic CO2 reduction: a review. Chemical Engineering Journal, 2024, 481: 148754

[24]

Niu J T , Liu H Y , Jin Y , Fan B , Qi W , Ran J . A density functional theory study of methane activation on MgO supported Ni9M1 cluster: role of M on C–H activation. Frontiers of Chemical Science and Engineering, 2022, 16(10): 1485–1492

[25]

Gould T D , Izar A , Weimer A W , Falconer J L , Medlin J W . Stabilizing Ni catalysts by molecular layer deposition for harsh, dry reforming conditions. ACS Catalysis, 2014, 4(8): 2714–2717

[26]

Cheng W , Wang Y S , Chen M Q , Liang D , Li C , Yang Z , Wang J . Hydrogen production from aqueous phase reforming of glycerol over attapulgite-supported nickel catalysts: effect of acid/base treatment and Fe additive. International Journal of Hydrogen Energy, 2022, 47(11): 7082–7099

[27]

Zheng J J , Impeng S , Liu J , Deng J , Zhang D . Mo promoting Ni-based catalysts confined by halloysite nanotubes for dry reforming of methane: insight of coking and H2S poisoning resistance. Applied Catalysis B: Environmental, 2024, 342: 123369

[28]

Oh J , Beck A , Goodman E D , Roling L T , Boucly A , Artiglia L , Abild-Pedersen F , van Bokhoven J A , Cargnello M . Colloidally engineered Pd and Pt catalysts distinguish surface- and vapor-mediated deactivation mechanisms. ACS Catalysis, 2023, 13(3): 1812–1822

[29]

Wen F L , Xu C , Huang N G , Wang T , Sun X , Li H , Zhang R , Xia G . Exceptional stability of spinel Ni-MgAl2O4 catalyst with ordered mesoporous structure for dry reforming of methane. International Journal of Hydrogen Energy, 2024, 69: 1481–1491

[30]

Gao Y S , Zhang C , Wang H P , Jiang L , Zhang D , Sun F , Ming S , Zhuang T , Lv Z . Sinter-resistant single core PtNi alloy@SiO2 channel (d ≈ 20 nm) catalysts for dry reforming of methane. ACS Sustainable Chemistry & Engineering, 2024, 12(37): 13986–13997

[31]

Yu F Y , Tao X Y N , Yu H R , Zhao T , Li M , Liu L , Wang H . Enhancing the sintering stability of NiCo/CeO2-Al2O3 catalyst in dry reforming of methane by shaping the ostwald ripening diffusion path. Chemical Engineering Journal, 2025, 504: 158725

[32]

Smoláková L , Kout M , Capek L , Rodriguez-Gomez A , Gonzalez-Delacruz V M , Hromádko L , Caballero A . Nickel catalyst with outstanding activity in the DRM reaction prepared by high temperature calcination treatment. International Journal of Hydrogen Energy, 2016, 41(20): 8459–8469

[33]

Bian Z F , Zhong W Q , Yu Y , Wang Z , Jiang B , Kawi S . Dry reforming of methane on Ni/mesoporous-Al2O3 catalysts: effect of calcination temperature. International Journal of Hydrogen Energy, 2021, 46(60): 31041–31053

[34]

Dieuzeide M L , Iannibelli V , Jobbagy M , Amadeo N . Steam reforming of glycerol over Ni/Mg/γ-Al2O3 catalysts. Effect of calcination temperatures. International Journal of Hydrogen Energy, 2012, 37(19): 14926–14930

[35]

Han B L , Zhao L , Wang F G , Xu L , Yu H , Cui Y , Zhang J , Shi W . Effect of calcination temperature on the performance of the Ni@SiO2 catalyst in methane dry reforming. Industrial & Engineering Chemistry Research, 2020, 59(30): 13370–13379

[36]

Seo J G , Youn M H , Chung J S , Song I K . Effect of calcination temperature of mesoporous nickel-alumina catalysts on their catalytic performance in hydrogen production by steam reforming of liquefied natural gas (LNG). Journal of Industrial and Engineering Chemistry, 2010, 16(5): 795–799

[37]

Özdemir H , Öksüzömer M A F , Gürkaynak M A . Effect of the calcination temperature on Ni/MgAl2O4 catalyst structure and catalytic properties for partial oxidation of methane. Fuel, 2014, 116: 63–70

[38]

Zhang Q L , Sun M H , Ning P , Long K , Wang J , Tang T , Fan J , Sun H , Yin L , Lin Q . Effect of thermal induction temperature on re-dispersion behavior of Ni nanoparticles over Ni/SBA-15 for dry reforming of methane. Applied Surface Science, 2019, 469: 368–377

[39]

Chaudhary P K , Deo G . Process and catalyst improvements for the dry reforming of methane. Chemical Engineering Science, 2023, 276: 118767

[40]

Seo B , Ko E H , Boo J , Kim M , Kang D , Park N K . CO2 hydrogenation on NixMg1−xAl2O4: a comparative study of MgAl2O4 and NiAl2O4. Catalysts, 2021, 11(9): 1026

[41]

Zou X , Rui Z , Song S , Ji H . Enhanced methane combustion performance over NiAl2O4-interface-promoted Pd/γ-Al2O3. Journal of Catalysis, 2016, 338: 192–201

[42]

Gao J J , Jia C M , Li J , Zhang M , Gu F , Xu G , Zhong Z , Su F . Ni/Al2O3 catalysts for CO methanation: effect of Al2O3 supports calcined at different temperatures. Journal of Energy Chemistry, 2013, 22(6): 919–927

[43]

Pamphile-Adrian A J , Passos F B , Florez-Rodriguez P P . Systematic study on the properties of nickel aluminate (NiAl2O4) as a catalytic precursor for aqueous phase hydrogenolysis of glycerol. Catalysis Today, 2022, 394: 499–509

[44]

Gil-Calvo M , Jiménez-González C , de Rivas B , Gutiérrez-Ortiz J I , López-Fonseca R . Effect of Ni/Al molar ratio on the performance of substoichiometric NiAl2O4 spinel-based catalysts for partial oxidation of methane. Applied Catalysis B: Environmental, 2017, 209: 128–138

[45]

Wen J J , Xie Y , Ma Y P , Sun H , Wang H , Liu M , Zhang Q , Chen J . Engineering of surface properties of Ni-CeZrAl catalysts for dry reforming of methane. Fuel, 2022, 308: 122008

[46]

Liu W Q , Bai P Y , Wei S L , Yang C , Xu L . Gadolinium changes the local electron densities of nickel 3d orbitals for efficient electrocatalytic CO2 reduction. Angewandte Chemie International Edition, 2022, 61(18): e202201166

[47]

Wang Y , Yao L , Wang Y , Wang S , Zhao Q , Mao D , Hu C . Low-temperature catalytic CO2 dry reforming of methane on Ni-Si/ZrO2 catalyst. ACS Catalysis, 2018, 8(7): 6495–6506

[48]

García-Diéguez M , Pieta I S , Herrera M C , Larrubia M A , Alemany L J . Nanostructured Pt- and Ni-based catalysts for CO2-reforming of methane. Journal of Catalysis, 2010, 270(1): 136–145

[49]

Kumar R , Kumar K , Pant K K , Choudary N V . Tuning the metal-support interaction of methane tri-reforming catalysts for industrial flue gas utilization. International Journal of Hydrogen Energy, 2020, 45(3): 1911–1929

[50]

Christensen K O , Chen D , Lodeng R , Holmen A . Effect of supports and Ni crystal size on carbon formation and sintering during steam methane reforming. Applied Catalysis A: General, 2006, 314(1): 9–22

[51]

Deng J , Yang B , Liu Y Y , Zhang X , Zheng J , Zhang D . Sintering- and coking-resistant nickel catalysts embedded in boron nitride supported nickel aluminate spinels for dry reforming of methane. Applied Catalysis A: General, 2022, 642: 118706

[52]

Zhang X , Deng J , Lan T , Shen Y , Zhong Q , Ren W , Zhang D . Promoting methane dry reforming over Ni catalysts via modulating surface electronic structures of BN supports by doping carbon. ACS Catalysis, 2022, 12(22): 14152–14161

[53]

Zhang J , Wang H , Dalai A K . Effects of metal content on activity and stability of Ni-Co bimetallic catalysts for CO2 reforming of CH4. Applied Catalysis A: General, 2008, 339(2): 121–129

[54]

Kim J H , Suh D J , Park T J , Kim K L . Effect of metal particle size on coking during CO2 reforming of CH4 over Ni–alumina aerogel catalysts. Applied Catalysis A: General, 2000, 197(2): 191–200

[55]

Al-Fatesh A S , Naeem M A , Fakeeha A H , Abasaeed A E . Role of La2O3 as promoter and support in Ni/γ-Al2O3 catalysts for dry reforming of methane. Chinese Journal of Chemical Engineering, 2014, 22(1): 28–37

[56]

Song P , Su T M , Luo Y H , Luo X , Ji H , Qin Z . Ni-Mg-Al catalysts for dry reforming of methane: effect of surface properties on coke formation and CO2 activation. Industrial & Engineering Chemistry Research, 2024, 63(37): 16077–16090

[57]

Debek R , Radlik M , Motak M , Galvez M E , Turek W , Da Costa P , Grzybek T . Ni-containing Ce-promoted hydrotalcite derived materials as catalysts for methane reforming with carbon dioxide at low temperature on the effect of basicity. Catalysis Today, 2015, 257: 59–65

[58]

Cholewins M C , Dixit M , Mpourmpakis G . Computational study of methane activation on γ-Al2O3. ACS Omega, 2018, 3(12): 18242–18250

[59]

Prins R . On the structure of γ-Al2O3. Journal of Catalysis, 2020, 392: 336–346

[60]

Huang J J , Yan Y , Saqline S , Liu W , Liu B . High performance Ni catalysts prepared by freeze drying for efficient dry reforming of methane. Applied Catalysis B: Environmental, 2020, 275: 119109

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