REFERENCES
1. Ishaq, H.; Dincer, I.; Crawford, C. A review on hydrogen production and utilization: Challenges and opportunities. Int. J. Hydrogen. Energy. 2022, 47, 26238-64.
2. Hermesmann, M.; Müller, T. Green, turquoise, blue, or grey? Environmentally friendly hydrogen production in transforming energy systems. Prog. Energy. Combust. Sci. 2022, 90, 100996.
3. Tong, S.; Miao, B.; Zhang, W.; Zhang, L.; Chan, S. H. Optimization of methane catalytic decomposition in a fluidized bed reactor: a computational approach. Energy. Convers. Manag. 2023, 297, 117719.
4. Zainal, B. S.; Ker, P. J.; Mohamed, H.; et al. Recent advancement and assessment of green hydrogen production technologies. Renew. Sustain. Energy. Rev. 2024, 189, 113941.
5. Shokrollahi, M.; Teymouri, N.; Ashrafi, O.; Navarri, P.; Khojasteh-salkuyeh, Y. Methane pyrolysis as a potential game changer for hydrogen economy: techno-economic assessment and GHG emissions. Int. J. Hydrogen. Energy. 2024, 66, 337-53.
6. Qian, J. X.; Chen, T. W.; Enakonda, L. R.; Liu, D. B.; Basset, J.; Zhou, L. Methane decomposition to pure hydrogen and carbon nano materials: State-of-the-art and future perspectives. Int. J. Hydrogen. Energy. 2020, 45, 15721-43.
7. Pinilla, J.; Utrilla, R.; Lázaro, M.; Moliner, R.; Suelves, I.; García, A. Ni- and Fe-based catalysts for hydrogen and carbon nanofilament production by catalytic decomposition of methane in a rotary bed reactor. Fuel. Process. Technol. 2011, 92, 1480-8.
8. Lua, A. C.; Wang, H. Y. Decomposition of methane over unsupported porous nickel and alloy catalyst. Appl. Catal. B. Environ. 2013, 132-133, 469-78.
9. Moghaddam, A. L.; Hejazi, S.; Fattahi, M.; et al. Methane pyrolysis for hydrogen production: navigating the path to a net zero future. Energy. Environ. Sci. 2025, 18, 2747-90.
10. Sun, E.; Zhai, S.; Kim, D.; et al. A semi-continuous process for co-production of CO2-free hydrogen and carbon nanotubes via methane pyrolysis. Cell. Rep. Phys. Sci. 2023, 4, 101338.
11. Bayat, N.; Meshkani, F.; Rezaei, M. Thermocatalytic decomposition of methane to COx-free hydrogen and carbon over Ni-Fe-Cu/Al2O3 catalysts. Int. J. Hydrogen. Energy. 2016, 41, 13039-49.
12. Ahmad, A.; Hamdani, I. R.; Srinivasakannan, C.; Al Shoaibi, A.; Hossain, M. M. Catalytic cracking of methane to hydrogen and carbon: scale-up perspective. Int. J. Hydrogen. Energy. 2024, 54, 1212-30.
13. Ahmed, H.; Alotibi, M. F.; Fakeeha, A. H.; et al. Hydrogen production via methane decomposition over alumina doped with titanium oxide-supported iron catalyst for various calcination temperatures. ChemistryOpen 2024, 13, e202300173.
14. Feng, F.; Song, G.; Xiao, J.; Shen, L.; Pisupati, S. V. Carbon deposition on Ni-based catalyst with TiO2 as additive during the syngas methanation process in a fluidized bed reactor. Fuel 2019, 235, 85-91.
15. Busillo, E.; Damizia, M.; De Filippis, P.; de Caprariis, B. Methane pyrolysis in molten media: the interplay of physical properties and catalytic activity on carbon and hydrogen production. J. Anal. Appl. Pyrolysis. 2024, 183, 106752.
16. Sanyal, A.; Malalasekera, W.; Bandulasena, H.; Wijayantha, K. Review of the production of turquoise hydrogen from methane catalytic decomposition: optimising reactors for sustainable hydrogen production. Int. J. Hydrogen. Energy. 2024, 72, 694-715.
17. Polo-garzon, F.; Fung, V.; Liu, X.; et al. Understanding the impact of surface reconstruction of perovskite catalysts on CH4 activation and combustion. ACS. Catal. 2018, 8, 10306-15.
18. Neagu, D.; Tsekouras, G.; Miller, D. N.; Ménard, H.; Irvine, J. T. In situ growth of nanoparticles through control of non-stoichiometry. Nat. Chem. 2013, 5, 916-23.
19. Jardiel, T.; Caldes, M.; Moser, F.; Hamon, J.; Gauthier, G.; Joubert, O. New SOFC electrode materials: the Ni-substituted LSCM-based compounds (La0.75Sr0.25)(Cr0.5Mn0.5-xNix)O3-δ and (La0.75Sr0.25)(Cr0.5-xNixMn0.5)O3-δ. Solid. State. Ionics. 2010, 181, 894-901.
20. Sun, H.; He, X.; Huang, X.; Gan, L. Modification of LSCM structure by anchoring alloy nanoparticles for efficient CO2 electrolysis. Energy. Fuels. 2024, 38, 3436-44.
21. Neagu, D.; Oh, T. S.; Miller, D. N.; et al. Nano-socketed nickel particles with enhanced coking resistance grown in situ by redox exsolution. Nat. Commun. 2015, 6, 8120.
22. Yu, J.; Liu, X.; Zhong, M.; et al. Suppression of Sr segregation in La0.6Sr0.4Co0.2Fe0.8O3-δ oxygen electrode via Ca doping for enhanced performance stability of reversible solid oxide cell. ACS. Appl. Mater. Interfaces. 2026, 18, 11409-20.
23. Koo, B.; Kim, K.; Kim, J. K.; Kwon, H.; Han, J. W.; Jung, W. Sr segregation in perovskite oxides: why it happens and how it exists. Joule 2018, 2, 1476-99.
24. Zhang, L.; Zhang, W.; Poh, C. K.; et al. Catalytic decomposition of methane: Ni-promoted perovskite oxide catalysts for turquoise hydrogen and carbon nanomaterials Co-production. Energy. Mater. 2025, 5, 500023.
25. Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865-8.
26. Monkhorst, H. J.; Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B. 1976, 13, 5188-92.
27. Jónsson, H.; Mills, G.; Jacobsen, K. W. Nudged elastic band method for finding minimum energy paths of transitions. In Classical and Quantum Dynamics in Condensed Phase Simulations, LERICI, Villa Marigola, July 7-18, 1997; Berne B. J.; Ciccotti, G.; Coker, D. F.; Eds.; World Scientific, 1997; pp 385-404.
28. Henkelman, G.; Uberuaga, B. P.; Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 2000, 113, 9901-4.
29. Vera, E.; Trillaud, V.; Metaouaa, J.; et al. Comparative study of exsolved and impregnated Ni nanoparticles supported on nanoporous perovskites for low-temperature CO oxidation. ACS. Appl. Mater. Interfaces. 2024, 16, 7219-31.
30. Flores-lasluisa, J.; Huerta, F.; Cazorla-amorós, D.; Morallón, E. LaNi1-xCoxO3 perovskites for application in electrochemical reactions involving molecular oxygen. Energy 2023, 273, 127256.
31. Khan, U. M.; Sarmad, Q.; Anwar, M.; et al. Synthesis of cobalt loaded double perovskite Sr2TiFeO6‐δ (STF) as a stable catalyst for enhanced hydrogen production via methane decomposition. Int. J. Energy. Res. 2021, 45, 20073-88.
32. Rudolph, B.; Tsiotsias, A. I.; Ehrhardt, B.; et al. Nanoparticle exsolution from nanoporous perovskites for highly active and stable catalysts. Adv. Sci. 2023, 10, e2205890.
33. Piazzolla, F.; Moraes, T. S.; Figueiredo, S. S.; et al. Exsolution of Ni nanoparticles from La0.4Sr0.4Ti0.8Ni0.2O3-δ perovskite for ethanol steam reforming. Catal. Today. 2025, 444, 115011.
34. Qiao, L.; Bi, X. Direct observation of Ni3+ and Ni2+ in correlated LaNiO3-δ films. EPL 2011, 93, 57002.
35. Whitten, A.; Guo, D.; Tezel, E.; Denecke, R.; Nikolla, E.; McEwen, J. S. Deconvoluting XPS spectra of La-containing perovskites from first-principles. JACS. Au. 2024, 4, 3104-17.
36. Barreau, M.; Salusso, D.; Zhang, J.; et al. Uncovering the critical function of lanthanum in CH4 production from CO2 using exsolved LaNiO3 perovskite catalysts. J. Mater. Chem. A. 2024, 12, 7605-21.
37. Vargas, N. F. C.; Alkathy, M. S.; Eiras, J. A.; Mastelaro, V. R.; Lente, M. H. Sintering‐driven effects on the band gap of (Pb,La)(Ti,Ni)O3 photovoltaic ceramics. J. Am. Ceram. Soc. 2021, 104, 2600-9.
38. Sun, Z.; Gong, Y.; Cheng, D.; Sun, Z. Reinforcing hydrogen and carbon nanotube co-production via Cr-O-Ni catalyzed methane decomposition. J. Mater. Chem. A. 2024, 12, 4893-902.
39. Sunding, M.; Hadidi, K.; Diplas, S.; Løvvik, O.; Norby, T.; Gunnæs, A. XPS characterisation of in situ treated lanthanum oxide and hydroxide using tailored charge referencing and peak fitting procedures. J. Electron. Spectrosc. Relat. Phenom. 2011, 184, 399-409.
40. Soltani, N.; Arcos, L. H.; Bahrami, A.; Carvayar, J. C. Structural changes in NiO-Ce0.8Sm0.2O2-x anode under reducing atmosphere. Mater. Charact. 2019, 150, 8-12.
41. Ning, X.; Wang, Z.; Zhang, Z. Fermi level shifting, charge transfer and induced magnetic coupling at La0.7Ca0.3MnO3/LaNiO3 interface. Sci. Rep. 2015, 5, 8460.
42. Hillebrecht, F. U.; Fuggle, J. C.; Bennett, P. A.; Zołnierek, Z.; Freiburg, C. Electronic structure of Ni and Pd alloys. II. X-ray photoelectron core-level spectra. Phys. Rev. B. 1983, 27, 2179-93.
43. Cao, P.; Tang, P.; Bekheet, M. F.; et al. Atomic-scale insights into nickel exsolution on LaNiO3 catalysts via in situ electron microscopy. J. Phys. Chem. C. 2022, 126, 786-96.
44. Wei, Y.; Zheng, Y.; Hu, Y.; et al. Controlling the cation exsolution of perovskite to customize heterostructure active site for oxygen evolution reaction. ACS. Appl. Mater. Interfaces. 2022, 14, 25638-47.
45. Anjaneyulu, C.; Naresh, G.; Kumar, V. V.; Tardio, J.; Rao, T. V.; Venugopal, A. Influence of rare earth (La, Pr, Nd, Gd, and Sm) metals on the methane decomposition activity of Ni-Al catalysts. ACS. Sustainable. Chem. Eng. 2015, 3, 1298-305.
46. Garbarino, G.; Kowalik, P.; Riani, P.; et al. Improvement of Ni/Al2O3 catalysts for low-temperature CO2 methanation by vanadium and calcium oxide addition. Ind. Eng. Chem. Res. 2021, 60, 6554-64.
47. Zhang, T.; Liu, Z.; Zhu, Y.; et al. Dry reforming of methane on Ni-Fe-MgO catalysts: influence of Fe on carbon-resistant property and kinetics. Appl. Catal. B. Environ. 2020, 264, 118497.
48. Osti, A.; Costa, S.; Rizzato, L.; Senoner, B.; Glisenti, A. Photothermal activation of methane dry reforming on perovskite-supported Ni-catalysts: impact of support composition and Ni loading method. Catal. Today. 2025, 449, 115200.
49. Helveg, S.; López-Cartes, C.; Sehested, J.; et al. Atomic-scale imaging of carbon nanofibre growth. Nature 2004, 427, 426-9.





