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In this study, hollow Ni\u2500NC (H\u2010Ni\u2010NC) was synthesized using nanoscale silica sphere templates and atomic Zn as a sacrificial pore\u2010former within the carbon shell. The optimized H\u2010Ni\u2010NC achieves a current density of \u22121.0 A cm\n                    <jats:sup>\u22122<\/jats:sup>\n                    with over 95% CO Faradaic efficiency in a flow cell. The high performance was attributed to the hollow sphere architecture enriched with gas\u2010permeable through\u2010pores. Notably, the Zn dosage selectively modulates the shell through\u2010porosity, without altering hollow sphere macrostructure or the active\u2010site structure, thereby enabling a systematic investigation of porosity effects. Finite\u2010element simulations provide a qualitative framework suggesting a trade\u2010off between reactant transport and active surface area with increasing porosity in hollow spherical catalysts. This work underscores that engineering of the nanoscale mass\u2010transport environment surrounding active sites plays a critical role in designing high\u2010efficiency electrocatalysts.\n                  <\/jats:p>","DOI":"10.1002\/adma.74095","type":"journal-article","created":{"date-parts":[[2026,7,13]],"date-time":"2026-07-13T06:34:28Z","timestamp":1783924468000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Porosity Engineering Within Ni\u2500N\u2500C Hollow Spheres for Ampere\u2010Level CO\n                    <sub>2<\/sub>\n                    Reduction Electrocatalysis"],"prefix":"10.1002","volume":"38","author":[{"given":"Jiage","family":"Yu","sequence":"first","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering Beijing University of Chemical Technology  Beijing P. R. 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