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Hydrogen production by dry reforming of methane in a catalytic reactor with La niobate-based hydrogen separation membrane

Nikita Eremeev, Dinara Altynbekova, Konstantin Valeev, Tamara Krieger, Arcady Ishchenko, Evgeny Suprun, Vladislav Sadykov, Yulia Bespalko

Abstract


Methane dry reforming is a promising approach for hydrogen production due to the simultaneous utilization of two greenhouse gases, methane and carbon dioxide. The implementation of methane dry reforming in catalytic reactors that utilize hydrogen separation membranes was demonstrated to enhance the process efficiency. This enhancement is attributed to the elimination of hydrogen, a product of the reaction, through the use of these membranes. The materials based on La1−xCaxNbO4±δ demonstrate considerable promise in applications involving hydrogen separation membranes due to their high protonic conductivity and stability under operational conditions. In this study, an asymmetric foam-supported membrane was fabricated and characterized in a hydrogen permeation test and a methane dry reforming reaction. The membrane is composed of a NiAl foam support, a La0.99Ca0.01NbO4±δ–NiCoOx dense permselective layer, and a NiRu/Pr0.3Ce0.35Zr0.35O2−δ catalytic layer. The membrane displays a high hydrogen permeation flux of ~2.5 ml H2/(cm2 min) at 700 °C in permeation tests and ~1.4 ml H2/(cm2 min) at 700 °C in methane dry reforming tests. Such a high hydrogen permeability can be attributed to the high protonic mobility of the permselective composite layer, as well as coupled electron and oxide ion transport. The conversion of methane and carbon dioxide is ~60% and ~80%, respectively. However, the membrane performance is demonstrated to slowly decline over a period of 100 hours of time-on-stream, which indicates that the composite and the catalyst materials require further development for more efficient application in catalytic membrane reactors for hydrogen production via methane dry reforming.

Keywords


lanthanum niobates; composites; hydrogen separation membranes; catalytic membrane reactors; hydrogen production; dry reforming of methane

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References


Naseem K, Qin F, Khalid F, Suo G, Zahra T, Chen Z, Javed Z. Essential parts of hydrogen economy: Hydrogen production, storage, transportation and application. Renew Sustain Energy Rev. 2025;210:115196. doi:10.1016/j.rser.2024.115196

Curcio E. Techno-economic analysis of hydrogen production: Costs, policies, and scalability in the transition to net-zero. Int J Hydrogen Energy. 2025;128:473–87. doi:10.1016/j.ijhydene.2025.04.013

Suwaileh W, Bicer Y, Al Hail S, Farooq S, Yunus RM, Rosman NN, Karajagi I. Exploring hydrogen fuel as a sustainable solution for zero-emission aviation: Production, storage, and engine adaptation challenges. Int J Hydrogen Energy. 2025;121:304–25. doi:10.1016/j.ijhydene.2025.03.348

Karibe H, Sair S, Faik A, Ait Ousaleh H. Electrified steam methane reforming: A review of heating technologies, challenges, and prospects. Int J Hydrogen Energy. 2025;133:200–13. doi:10.1016/j.ijhydene.2025.04.475

Szablowski L, Wojcik M, Dybinski O. Review of steam methane reforming as a method of hydrogen production. Energy. 2025;316:134540. doi:10.1016/j.energy.2025.134540

Fazeli R, Longden T, Beck FJ. Dynamics of price-based competition between blue and green hydrogen with net zero emissions targets. Renew Sustain Energy Rev. 2025;210:115244. doi:10.1016/j.rser.2024.115244

Hu T, Song Y, Zhang X, Lin S, Liu P, Zheng C, Gao X. A mini review for hydrogen production routes toward carbon neutrality. Propul Energy. 2025;1(1):1–20. doi:10.1007/s44270-024-00004-4

Wang Y, Li R, Zeng C, Sun W, Fan H, Ma Q, Zhao T S. Recent research progress of methane dry reforming to syngas. Fuel. 2025;398:135535. doi:10.1016/j.fuel.2025.135535

Agún B, Abánades A. Comprehensive review on dry reforming of methane: Challenges and potential for greenhouse gas mitigation. Int J Hydrogen Energy. 2025;103:395–414. doi:10.1016/j.ijhydene.2025.01.160

Osazuwa OU, Vo D VN, Ng KH. Hydrogen energy from biogas (CO2 and CH4) via dry reforming of methane: A review on confined Ni-catalysts. Process Saf Environ Prot. 2025;198:107045. doi:10.1016/j.psep.2025.107045

Sharifnattaj A, Ghaziasgar S, Bahadori Y, Saidi M. Recent progress in catalysts development of dry reforming of methane process: Review of active phases and supports of catalyst. Mol Catal. 2025;582:115060. doi:10.1016/j.mcat.2025.115060

Dalanta F, Handoko DT, Hadiyanto H, Kusworo TD. Recent implementations of process intensification strategy in membrane-based technology: A review. Chem Eng Res Design. 2024;202:74–91.doi:10.1016/j.cherd.2023.12.014

Guerrero-Pérez MO. Perspectives and state of the art of membrane separation technology as a key element in the development of hydrogen economy. Membranes. 2024;14(11):228. doi:10.3390/membranes14110228

Al Masud MA, Khuu NH, Sanyal O, Tian Y. Advances in membrane-assisted reactors: An integrative review for modeling and experiments. Sep Purif Technol. 2025;371:133095. doi:10.1016/j.seppur.2025.133095

Casadio S, Gondolini A, Mercadelli E, Sanson A. Advances and prospects in manufacturing of ceramic oxygen and hydrogen separation membranes. Renew Sustain Energy Rev. 2024;200:114600. doi:10.1016/j.rser.2024.114600

Zhang Z, Zhou W, Wang T, Gu Z, Zhu Y, Liu Z, Wu Z, Zhang G, Jin W. Ion–conducting ceramic membrane reactors for the conversion of chemicals. Membranes. 2023;13(7):621. doi:10.3390/membranes13070621

Liu C, Zhang X, Zhai J, Li X, Guo X, He G, Research progress and prospects on hydrogen separation membranes. Clean Energy. 2023;7(1):217–41. doi:10.1093/ce/zkad014

Fan L, Luo W, Fan Q, Hu Q, Jin Y, Chiu T W, Lund PD. Status and outlook of solid electrolyte membrane reactors for energy, chemical, and environmental applications. Chem Sci. 2025;16(16):6620–87. doi:10.1039/D4SC08300H

Jokar SM, Farokhnia A, Gonçalves MC, Zare F, Parvasi P, Tavakolian M, Basile A. Hydrogen production from refinery outputs utilizing palladium membrane reactors: A review. Int J Hydrogen Energy. 2025;136:229–51. doi:10.1016/j.ijhydene.2025.04.493

Qiao L, Kang Z, Li Z, Feng Y, Sun D. Crystalline porous material based membranes for hydrogen separation. Fuel. 2024;359:130477. doi:10.1016/j.fuel.2023.130477

Li P, Li T, Xiao R. A review of catalytic hydrogen production using metallic membrane reactors. Int J Hydrogen Energy. 2025;130:176–90. doi:10.1016/j.ijhydene.2025.04.323

Hashmi SAM, Chuah CY, Yang E, Poon WC. Advances in H2-selective metallic membranes for pre-combustion CO2 capture: A critical review. Carbon Capture Sci Technol. 2024;13:100247. doi:10.1016/j.ccst.2024.100247

Wang J, Yuan C, Li C, Geng G, Song J, Yang N, Kawi S, Sunarso J, Tan X, Liu S. Nickel-based metallic membranes for hydrogen production in membrane reactor: A brief overview. Sep Purif Technol. 2024;358B:130435. doi:10.1016/j.seppur.2024.130435

Eikeng E, Makhsoos A, Pollet BG. Critical and strategic raw materials for electrolysers, fuel cells, metal hydrides and hydrogen separation technologies. Int J Hydrogen Energy. 2024;71:433–64. doi:10.1016/j.ijhydene.2024.05.096

Sadykov V, Pikalova E, Sadovskaya E, Shlyakhtina A, Filonova E, Eremeev N. Design of mixed ionic-electronic materials for permselective membranes and solid oxide fuel cells based on their oxygen and hydrogen mobility. Membranes. 2023;13(8):698. doi.10.3390/membranes13080698

Yang D, Xu P, Xiang Q, Liao N. Atomic-level insights into permeability and selectivity of V-Ni, V-Ni-Ti and Ta-Nb alloys membranes for highly selective hydrogen separation. Int J Hydrogen Energy. 2025;106:546–52. doi:10.1016/j.ijhydene.2025.01.465

Medvedev DA. Current drawbacks of proton-conducting ceramic materials: How to overcome them for real electrochemical purposes. Curr Opin Green Sustain Energy. 2021;32:100549. doi:10.1016/j.cogsc.2021.100549

Cheng S, Li X, Huang X, Ling Y, Liu S, Li T. Hydrogen separation via proton conducting ceramic membranes: A review. Int J Hydrogen Energy. 2024;70:654–65. doi:10.1016/j.ijhydene.2024.05.181

Regalado Vera CY, Ding H, Peterson D, Gibbons WT, Zhou M, Ding D. A mini-review on proton conduction of BaZrO3-based perovskite electrolytes. J Phys Energy. 2021;3(3):032019. doi:10.1088/2515-7655/ac12ab

Hossain MK, Chanda R, El-Denglawey A, Emrose T, Rahman MT, Biswas MC, Hashizume K. Recent progress in barium zirconate proton conductors for electrochemical hydrogen device applications: A review. Ceram Int. 2021;47(17):23725–48. doi:10.1016/j.ceramint.2021.05.167

Winiarz P, Covarrubias MSC, Sriubas M, Bockute K, Miruszewski T, Skubida W, Jaworski D, Laukaitis G, Gazda M. Properties of barium cerate-zirconate thin films. Crystals. 2021;11(8):1005. doi:10.3390/cryst11081005

Yılmaz EE, Koşma EB, Figen HE, Elibol MK. Physicochemical characterization of calcium-doped barium zirconate perovskites for hydrogen-induced systems and their life cycle assessment. Int J Hydrogen Energy. 2025;143:1267–78. doi:10.1016/j.ijhydene.2025.01.313

Shahid M. Recent advances in protonconducting electrolytes for solid oxide fuel cells. Ionics. 2022;28(8):3583–601. doi:10.1007/s11581-022-04629-w

Sun S, Tang Q, Zhang K, Wen Y, Billings A, Huang K. A focused review on structures and ionic conduction mechanisms in inorganic solid-state proton and hydride anion conductors. Mater Adv. 2023;4(2):389–407. doi:10.1039/D2MA01003H

Fop S. Solid oxide proton conductors beyond perovskites. J Mater Chem A. 2021;9(35):18836–56. doi:10.1039/D1TA03499E

Yang X, Fernández-Carrión AJ, Kuang X. Oxide ion-conducting materials containing tetrahedral moieties: Structures and conduction mechanisms. Chem Rev. 2023;123(15):9356–96. doi:10.1021/acs.chemrev.2c00913

Sadykov VA, Sadovskaya EM, Eremeev NF, Skriabin PI, Krasnov AV, Bespalko YuN, Pavlova SN, Fedorova YuE, Pikalova EYu, Shlyakhtina AV. Oxygen mobility in materials for solid oxide fuel cells and catalytic membranes (review). Russ J Electrochem. 2019;55(8):701–18. doi:10.1134/S1023193519080147

Guskov VN, Gavrichev KS. Thermal expansion, heat capacity, and thermodynamic properties of monoclinic lanthanide orthotantalates: A review. Russ J Inorg Chem. 2021;66(13):1947–72. doi:10.1134/S0036023621130088

Altynbekova DT, Massalimova BK, Bespalko YuN, Sadykov VA. Obzor electrolitov na osnova ortoniobata lantana. Struktura i protonnaya provodimost’ [Review of lanthanum orthoniobate-based electrolytes. Structure and proton conductivity]. Bul LN Gumilyov ENU Chem Geogr Ecol Ser. 2020;133(4):18–34. Russian. doi:10.32523/2616-6771-2020-133-4-18-34

Haugsrud R, Norby T. Proton conduction in rare-earth ortho-niobates and ortho-tantalates. Nat Mater. 2006;5(3):193–6. doi:10.1038/nmat1591

Fjeld H, Toyoura K, Haugsrud R, Norby T. Proton mobility through a second order phase transition: Theoretical and experimental study of LaNbO4. Phys Chem Chem Phys. 2010;12(35):10313–9. doi:10.1039/C002851G

Wang R, Byrne C, Tucker MC. Assessment of co-sintering as a fabrication approach for metal-supported proton-conducting solid oxide cells. Solid State Ionics. 2019;332:25–33. doi:10.1016/j.ssi.2019.01.004

Canu G, Buscaglia V, Ferrara C, Mustarelli P, Patrício SG, Rondão AIB, Tealdi C, Marques FMB. Oxygen transport and chemical compatibility with electrode materials in scheelite-type LaWxNb1−xO4+x/2 ceramic electrolyte. J Alloy Compd. 2017;697:392–400. doi:10.1016/j.jallcom.2016.12.111

Sadykov VA, Bespalko YuN, Krasnov AV, Skriabin PI, Lukashevich AI, Fedorova YuE, Sadovskaya EM, Eremeev NF, Krieger TA, Ishchenko AV, Belyaev VD, Uvarov NF, Ulihin AS, Skovorodin IN. Novel proton-conducting nanocomposites for hydrogen separation membranes. Solid State Ionics. 2018;322:69–78. doi:10.1016/j.ssi.2018.05.003

Altynbekova D, Bespalko Yu, Valeev K, Eremeev N, Sadovskaya E, Krieger T, Ulihin A, Uhina A, Massalimova B, Simonov M, Sadykov V. Simple approach to the fabrication of lanthanum orthoniobates and nanocomposites with Ni, Cu, and Co metal nanoparticles using supercritical isopropanol. J Compos Sci. 2022;6(9):243. doi:10.3390/jcs6090243

Sadykov VA, Bobrova LN, Mezentseva NV, Pavlova SN, Fedorova YuE, Bobin AS, Vostrikov ZYu, Glazneva TS, Smirnova MYu, Sazonova NN, Rogov VA, Ishchenko AV, Marin GB, Thybaut J, Galvita VV, Schuurman Y, Mirodatos C. Methane dry reforming on nanocomposite catalysts: Design, kinetics, and mechanism. In: Small-Scale Gas to Liquid Fuel Synthesis. CRC Press; 2015. pp. 315–75. doi:10.1201/b18075-16

Sadykov VA, Eremeev NF, Sadovskaya EM, Fedorova JE, Arapova MV, Bobrova LN, Ishchenko AV, Krieger TA, Melgunov MS, Glazneva TS, Kaichev VV, Rogov VA. Approaches to the design of efficient and stable catalysts for biofuel reforming into syngas: Doping the mesoporous MgAl2O4 support with transition metal cations. Dalton Trans. 2023;52(25):8756–69. doi:10.1039/d3dt00830d

Sadykov V, Pavlova S, Fedorova J, Bobin A, Fedorova V, Simonov M, Ishchenko A, Krieger T, Melgunov M, Glazneva T, Larina T, Kaichev V, Roger A C. Structured catalysts with mesoporous nanocomposite active components for transformation of biogas/biofuels into syngas. Catal Today. 2021;379:166–80. doi:10.1016/j.cattod.2020.10.017

Sadykov VA, Simonov MN, Eremeev NF, Mezentseva NV. Modern trends and problems related to design of catalysts for biofuels transformation into syngas and hydrogen. In: Current Perspective to Physical Science Research. Vol.8. B P International; 2024. pp. 54–94. doi:10.9734/bpi/cppsr/v8/8018e

Eremeev NF, Hanna SA, Sadykov VA, Bespalko YuN. Ethanol dry reforming into synthesis gas: Effect of oxygen mobility and reactivity. Sustain Energy Fuels. 2025. [Cited 2025] doi:10.1039/D5SE00359H

Altynbekova DT, Massalimova BK, Bespalko YuN, Valeev KR, Krieger TA, Sadykov VA. Synthesis of nanocrystalline complex oxides in supercritical alcohols. News Natl Acad Sci Republic Kazakhstan Ser Chem Technol. 2020;4(442).6–13. doi:10.32014/2020.2518-1491.58

Bespalko Yu, Smal E, Simonov M, Valeev K, Fedorova V, Krieger T, Cherepanova S, Ishchenko A, Rogov V, Sadykov V. Novel Ni/Ce(Ti)ZrO2 catalysts for methane dry reforming prepared in supercritical alcohol media. Energies. 2020;13(13):3365. doi:10.3390/en13133365

Stoyanovskii VO, Vedyagin AA, Volodin AM, Bespalko YuN. Effect of carbon shell on stabilization of single-phase lanthanum and praseodymium hexaaluminates prepared by a modified Pechini method. Ceram Int. 2020;46(18):29150–9. doi:10.1016/j.ceramint.2020.08.088

Eremeev NF, Hanna SA, Sadovskaya EM, Leonova AA, Bulavchenko OA, Ishchenko AV, Prosvirin IP, Sadykov VA, Bespalko YuN. Catalysts for ethanol dry reforming based on high-entropy perovskites. J Catal. 2025;445:116028. doi:10.1016/j.jcat.2025.116028

Lopatin MYu, Sadovskaya EM, Ksenz AS, Vorobyova AA, Boltalin AI, Knotko AV, Sorokina NM, Shatalova TB, Petukhov DI, Fedorova YuE, Eremeev NF, Sadykov VA, Morozov IV, Fedorova AA. A new approach to lanthanum silicates with apatite structure synthesis using β-cyclodextrin. Colloids Surf A: Physicochem Eng Asp. 2025;708:135979. doi:10.1016/j.colsurfa.2024.135979

Sadykov V, Zarubina V, Pavlova S, Krieger T, Alikina G, Lukashevich A, Muzykantov V, Sadovskaya E, Mezentseva N, Zevak E, Belyaev V, Smorygo O. Design of asymmetric multilayer membranes based on mixed ionic–electronic conducting composites supported on Ni–Al foam substrate. Catal Today. 2010;156(3–4):173–80. doi:10.1016/j.cattod.2010.07.030

Bespalko Yu, Sadykov V, Eremeev N, Skryabin P, Krieger T, Sadovskaya E, Bobrova L, Uvarov N, Lukashevich A, Krasnov A, Fedorova Yu. Synthesis of tungstates/Ni0.5Cu0.5O nanocomposite materials for hydrogen separation cermet membranes. Compos Struct. 2018;202:1263–74. doi:10.1016/j.compstruct.2018.06.004

Sadykov VA, Eremeev NF, Fedorova YuE, Krasnov AV, Bobrova LN, Bespalko YuN, Lukashevich AI, Skriabin PI, Smorygo OL, Van Veen AC. Design and performance of asymmetric supported membranes for oxygen and hydrogen separation. Int J Hydrogen Energy. 2021;46(38):20222–39. doi:10.1016/j.ijhydene.2020.01.106

Eremeev N, Krasnov A, Bespalko Yu, Bobrova L, Smorygo O, Sadykov V. An experimental performance study of a catalytic membrane reactor for ethanol steam reforming over a metal honeycomb catalyst. Membranes. 2021;11(10):790. doi:10.3390/membranes11100790

Ververs WJR, Ongis M, Arratibel A, Di Felice L, Gallucchi F. On the modeling of external mass transfer phenomena in Pd-based membrane separations. Int J Hydrogen Energy. 2024;71:1121–33. doi:10.1016/j.ijhydene.2024.04.337

Ivanova M, Ricote S, Meulenberg WA, Haugsrud R, Ziegner M. Effects of A- and B-site (co-)acceptor doping on the structure and proton conductivity of LaNbO4. Solid State Ionics. 2012;213:45–52. doi:10.1016/j.ssi.2011.06.012

Palisaitis J, Ivanova ME, Meulenberg WA, Guillon O, Mayer J. Phase homogeneity analysis of La0.99Sr0.01Nb0.99Al0.01O4−δ and La0.99Ca0.01Nb0.99Ti0.01O4−δ proton conductors by high-resolution STEM and EELS. J Eur Ceram Soc. 2015;35(5):1517–25. doi:10.1016/j.jeurceramsoc.2014.11.010

Bobrova L, Eremeev N, Vernikovskaya N, Sadykov V, Smorygo O. Effect of asymmetric membrane structure on hydrogen transport resistance and performance of a catalytic membrane reactor for ethanol steam reforming. Membranes. 2021;11(5):332. doi:10.3390/membranes11050332

Bobrova L, Vernikovskaya N, Eremeev N, Sadykov V. Model-based performance analysis of membrane reactor with ethanol steam reforming over a monolith. Membranes. 2022;12(8):741. doi:10.3390/membranes12080741

Sadykov VA, Krasnov AV, Fedorova YuE, Lukahevich AI, Bespalko YuN, Eremeev NF, Skriabin PI, Valeev KR, Smorygo OL. Novel nanocomposite materials for oxygen and hydrogen separation membranes. Int J Hydrogen Energy. 2020;45(25):13575–85. doi:10.1016/j.ijhydene.2018.02.182

Cheng S, Gupta VK, Lin JYS. Synthesis and hydrogen permeation properties of asymmetric proton-conducting ceramic membranes. Solid State Ionics. 2005;176(35–36):2653–62. doi:10.1016/j.ssi.2005.07.005

Zhan S, Zhu X, Ji B, Wang W, Zhang X, Wang J, Yang W, Lin L. Preparation and hydrogen permeation of SrCe0.95Y0.05O3−δ asymmetrical membranes. J Membr Sci. 2009;340(1–2):241–8. doi:10.1016/j.memsci.2009.05.037

Zhu Z, Yan L, Liu H, Sun W, Zhang Q, Liu W. A mixed electronic and protonic conducting hydrogen separation membrane with asymmetric structure. Int J Hydrogen Energy. 2012;37(17):12708–13. doi:10.1016/j.ijhydene.2012.06.033

Ua-amnueychai W, Asada K, Hanamura K. Asymmetric lanthanum doped ceria membrane with proton conductive and hydrogen separation capability for solid oxide fuel cell. Eng J. 2015;19(3):49–60. doi:10.4186/ej.2015.19.3.49

Gondolini A, Bartoletti A, Mercadelli E, Gramazio P, Fasolini A, Basile F, Sanson A. Development and hydrogen permeation of freeze-cast ceramic membrane. J Membr Sci. 2023;684:121865. doi:10.1016/j.memsci.2023.121865

Hung I M, Chiang Y J, Jang JS C, Lin J C, Lee S W, Chang J K, Hsi C S. The proton conduction and hydrogen permeation characteristic of Sr(Ce0.6Zr0.4)0.85Y0.15O3−δ ceramic separation membrane. J Eur Ceram Soc. 2015;35(1):163–70. doi:10.1016/j.jeurceramsoc.2014.08.019

Xing W, Syvertsen GE, Grande T, Li Z, Haugsrud R. Hydrogen permeation, transport properties and microstructure of Ca-doped LaNbO4 and LaNb3O9 composites. J Membr Sci. 2012;415–6:878–85. doi:10.1016/j.memsci.2012.06.008

Chen L, Liu L, Xue J, Zhuang L, Wang H. Asymmetric membrane structure: An efficient approach to enhance hydrogen separation performance. Sep Purif Technol. 2018;207:363–9. doi:10.1016/j.seppur.2018.06.066

Sadykov V, Sadovskaya E, Eremeev N, Kolchugin A, Filonova E, Tsvinkinberg V, Zhulanova T, Pikalova E. Novel materials based on Ruddlesden–Popper phases for solid oxide fuel cells and oxygen separation membranes: Fundamentals of oxygen transport. Chim Tech Acta. 2025;12(3):12304. doi:10.15826/chimtech.2025.12.3.04

Shelekhin AB, Dixon AG, Ma YH. Theory of gas diffusion and permeation in inorganic molecular‐sieve membranes. AIChE J. 1995;41(1):58–67. doi:10.1002/aic.690410107

Tsuru T, Shintani H, Yoshioka T, Asaeda M. A bimodal catalytic membrane having a hydrogen-permselective silica layer on a bimodal catalytic support: Preparation and application to the steam reforming of methane. Appl Catal A Gen. 2006;302(1):78–85. doi:10.1016/j.apcata.2005.12.029

Vermaak L, Neomagus HWJP, Bessarabov DG. Recent advances in membrane-based electrochemical hydrogen separation: A review. Membranes. 2021;11(2):127. doi:10.3390/membranes11020127

Cheng H. Dual-phase mixed protonic-electronic conducting hydrogen separation membranes: A review. Membranes. 2022;12(7):647. doi:10.3390/membranes12070647

Matsuka M, Braddock RD, Matsumoto H, Sakai T, Agranovski IE, Ishihara T. Experimental and theoretical studies of hydrogen permeation for doped strontium cerates. Solid State Ionics. 2010;181(29–30):1328–35. doi:10.1016/j.ssi.2010.07.002

Liang W, Zhang Y, Hu T, Jiang H. Enhanced H2 production by using La5.5WO11.25−δ–La0.8Sr0.2FeO3−δ mixed oxygen ion-proton-electron triple-conducting membrane. Int J Hydrogen Energy. 2021;46(66):33143–51. doi:10.1016/j.ijhydene.2021.07.134

Fontaine M L, Norby T, Larring Y, Grande T, Bredesen R. Oxygen and hydrogen separation membranes based on dense ceramic conductors. In: Membrane Science and Technology, Volume 13: Inorganic Membranes: Synthesis, Characterization and Applications. Elsevier; 2008. pp. 401–58. doi:10.1016/S0927-5193(07)13010-2

Shelepova E, Vedyagin A, Sadykov V, Mezentseva N, Fedorova Yu, Smorygo O, Klenov O, Mishakov I. Theoretical and experimental study of methane partial oxidation to syngas in catalytic membrane reactor with asymmetric oxygen-permeable membrane. Catal Today. 2016;268:103–10. doi:10.1016/j.cattod.2016.01.005

Abdel Karim Aramouni N, Zeaiter J, Kwapinski W, Ahmad MN. Thermodynamic analysis of methane dry reforming: Effect of the catalyst particle size on carbon formation. Energy Convers Manage. 2017;150:614–22. doi:10.1016/j.enconman.2017.08.056

Awad MM, Kotob E, Ahmed Taialla O, Hussain I, Ganiyu SA, Alhooshani K. Recent developments and current trends on catalytic dry reforming of methane: Hydrogen production, thermodynamics analysis, techno feasibility, and machine learning. Energy Convers Manage. 2024;304:118252. doi:10.1016/j.enconman.2024.118252

Wang B, Lu X, Lundin S TB, Kong H, Wang J, Su B, Wang H. Thermodynamic analysis and optimization of solar methane dry reforming enhanced by chemical hydrogen separation. Energy Convers Manage. 2022;268:116050. doi:10.1016/j.enconman.2022.116050

Bespalko YuN, Fedorova VE, Smal EA, Arapova MV, Valeev KR, Krieger TA, Ishchenko AV, Sadykov VA, Simonov MN. Ni and Ni–Co catalysts based on mixed Ce–Zr oxides synthesized in isopropanol medium for dry reforming of methane. Russ J Phys Chem B. 2022;16(8):1384–96. doi:10.1134/S1990793122080048

Arapova M, Smal E, Bespalko Yu, Valeev K, Fedorova V, Hassan A, Bulavchenko O, Sadykov V, Simonov M. Methane dry reforming catalysts based on Pr-doped ceria–zirconia synthesized in supercritical propanol. Energies. 2023;16(12):4729. doi:10.3390/en16124729

Durán P, Sanz-Martínez A, Soler J, Menéndez M, Herguido J. Pure hydrogen from biogas: Intensified methane dry reforming in a two-zone fluidized bed reactor using permselective membranes. Chem Eng J. 2019;370:772–81. doi:10.1016/j.cej.2019.03.199

Wang J, Shao B, Li C, Song J, Meng B, Meng X, Yang N, Kawi S, Sunarso J, Tan X, Liu S. Preparation of BCYF0.10–YDC/BCYF0.10–Ni dual-layer hollow fiber membrane for dry reforming of methane and hydrogen purification. Catal Sci Technol. 2023;13(16):4673–83. doi:10.1039/D3CY00595J

Li J, Yoon H, Wachsman ED. Carbon dioxide reforming of methane in a SrCe0.7Zr0.2Eu0.1O3−δ proton conducting membrane reactor. Int J Hydrogen Energy. 2012;37(24):19125–32. doi:10.1016/j.ijhydene.2012.09.134

Nishimura A, Ito S, Ichikawa M, Kolhe ML. Impact of thickness of Pd/Cu membrane on performance of biogas dry reforming membrane reactor utilizing Ni/Cr catalyst. Fuels. 2024;5(3):439–57. doi:10.3390/fuels5030024

Nishimura A, Ichikawa M, Hayakawa T, Yamada S, Ichii R, Kolhe ML. Impact of membrane thickness on characteristics of biogas dry reforming membrane reactor using Pd/Cu membrane and Ni/Cr/Ru catalyst. Fuels. 2025;6(1):18. doi:10.3390/fuels6010018

Bosko ML, Múnera JF, Lombardo EA, Cornaglia LM. Dry reforming of methane in membrane reactors using Pd and Pd–Ag composite membranes on a NaA zeolite modified porous stainless steel support. J Membr Sci. 2010;364(1–2):17–26. doi:10.1016/j.memsci.2010.07.039

Sumrunronnasak S, Tantayanon S, Kiatgamolchai S, Sukonket T. Improved hydrogen production from dry reforming reaction using a catalytic packed-bed membrane reactor with Ni-based catalyst and dense PdAgCu alloy membrane. Int J Hydrogen Energy. 2016;41(4):2621–30. doi:10.1016/j.ijhydene.2015.10.129

Irusta S, Múnera J, Carrara C, Lombardo EA, Cornaglia LM. A stable, novel catalyst improves hydrogen production in a membrane reactor. Appl Catal A Gen. 2005;287(2):147–58. doi:10.1016/j.apcata.2005.03.018

Fontana AD, Faroldi B, Cornaglia LM, Tarditi AM. Development of catalytic membranes over PdAu selective films for hydrogen production through the dry reforming of methane. Mol Catal. 2020;481:100643. doi:10.1016/j.mcat.2018.07.018

Pati S, Das S, Dewangan N, Jangam A, Kawi A. Facile integration of core–shell catalyst and Pd-Ag membrane for hydrogen production from low-temperature dry reforming of methane. Fuel. 2023;333(2):126433. doi:10.1016/j.fuel.2022.126433

Singh PP, P A, Kamaliny S, Ray K, Sengupta S. The pivotal role of oxygen vacancy and surface hydroxyl in the adsorption and activation of CO2 on ceria-zirconia mixed oxide. Mol Catal. 2024;555:113855. doi:10.1016/j.mcat.2024.113855

Sun J, Yamaguchi D, Tang L, Chiang K. Unravelling carbon formation behaviour and long-term stability of dry reforming of methane over Ru-doped ceria-zirconia catalyst. J CO2 Util. 2025;97:103131. doi:10.1016/j.jcou.2025.103131

Peng Y, Si X L, Liu Z P. Abundance of low-energy oxygen vacancy pairs dictates the catalytic performance of cerium-stabilized zirconia. J Am Chem Soc. 2024;146(15):10822–32. doi:10.1021/jacs.4c01285

Pikalova EYu, Kalinina EG. Solid oxide fuel cells based on ceramic membranes with mixed conductivity: Improving efficiency. Russ Chem Rev. 2021;90(6):703–49. doi:10.1070/RCR4966

Pikalova E, Kalinina E, Pikalova N. Recent advances in electrophoretic deposition of thin-film electrolytes for intermediate-temperature solid oxide fuel cells. Electrochem Mater Technol. 2023;2(1):20232011. doi:10.15826/elmattech.2023.2.011

Smal E, Bespalko Yu, Arapova M, Fedorova V, Valeev K, Eremeev N, Sadovskaya E, Krieger T, Glazneva T, Sadykov V, Simonov M. Carbon formation during methane dry reforming over Ni-containing ceria-zirconia catalysts. Nanomaterials. 2022;12(20):3676. doi:10.3390/nano12203676

Alvarez J, Valderrama G, Pietri E, Pérez-Zurita MJ, Urbina de Navarro C, Falabella Sousa-Aguiar E, Goldwasser MR. Ni–Nb-based mixed oxides precursors for the dry reforming of methane. Top Catal. 2011;54(1–4):170–8. doi:10.1007/s11244-011-9636-7

Chen S, Yang B. Activity and stability of alloyed NiCo catalyst for the dry reforming of methane: A combined DFT and microkinetic modeling study. Catal Today. 2022;400–1:59–65. doi:10.1016/j.cattod.2021.11.016

Tang D, Li JZ, Cao D, An Y, Song J, Shen X, Zhang X. NiCo Alloy catalysts for low-temperature solar-driven methane dry reforming: Insights into CH4 activation and carbon accumulation. ACS Appl Mater Interfaces. 2025;17(2):3457–66. doi:10.1021/acsami.4c19523

Zheng Y, Lu Z, Shi Z, Wang L, Yang S, Cao R, Wa G, Zhou X, Yang Y, Sheng C, Zhou Y, Zou Z. Unique NiCo bimetal boosting 98% CH4 selectivity and high catalysis stability for photothermal CO2 hydrogenation. Nanoscale. 2025;17(10):5770–7. doi:10.1039/D4NR05471G




DOI: https://doi.org/10.15826/chimtech.2025.12.3.11

Copyright (c) 2025 Nikita Eremeev, Dinara Altynbekova, Konstantin Valeev, Tamara Krieger, Arcady Ishchenko, Evgeny Suprun, Vladislav Sadykov, Yulia Bespalko

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Chimica Techno Acta, 2014–2025
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