Xue, QiangqiangQian, ShuairenLim, Kang HuiWee, Melvin Xin JieNie, KaiqiCheng, ShuwenChen, XiaohanChirawatkul, PraeJohannessen, BerntYan, BinhangYin, ZongyouWang, YujunLuo, GuangshengGates, Bruce C.Kawi, Sibudjing2026-03-212026-03-210002-7863PubMed:41061106ORCID:/0009-0002-3545-0610/work/208943294https://hdl.handle.net/1885/733807592Catalytic methane decomposition provides a potentially viable route to low-cost, COx-free H2from this abundant source. A remaining challenge is to facilitate the needed low-temperature C–H bond activation with high catalytic activity and stability. We now report the design and synthesis of supported Ni catalysts that address these limitations; they consist of silica-supported Ni nanoparticles ensheathed in nanoscale TiO2shells, forming an embedded core–shell structure that provides catalyst stability, maintaining a H2site-time yield of 3.6 mol/gNi/h at a space velocity of 24000 mL gcat–1·h–1at 550 °C for 6 h on stream in a flow reactor. In contrast, a comparable catalyst without the sheath deactivated after only 2.5 h, being characterized by a Ni-extracting tip-growth mechanism of coproduct carbon nanotube formation that destroyed the catalyst. An advantage of the ensheathed catalyst is that it facilitates a Ni-sparing base-growth mechanism. Infrared and Raman spectra, combined with other catalyst characterization data and calculations at the level of density functional theory, show that the TiO2sheaths barely hinder the C–H bond cleavage and carbon nanotube formation on the underlying nickel, while providing the advantages stated above. We postulate that these results provide guidance for the synthesis of catalysts for low-temperature H2production and related reactions requiring C–H bond activation.This work was financially supported by the National Research Foundation, Singapore, and A*STAR under its Low-Carbon Energy Research (LCER) Funding Initiative (FI) Project (U2102d2011, WBS: A-8000278-00-00). The XAFS characterization was supported by the Synchrotron Light Research Institute (Public Organization, SLRI) and the Australian Synchrotron (ANSTO).17en©2025 The authors2025-10-2210.1021/jacs.5c10017105019497307