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However, this transformation suffers from sluggish kinetics and insufficient hydrogenation, leading to poor selectivity and efficiency. Herein, we report the deposition of Cu\n                    <jats:sub>4<\/jats:sub>\n                    I\n                    <jats:sub>4<\/jats:sub>\n                    nanocluster onto TiO\n                    <jats:sub>2<\/jats:sub>\n                    (Cu\n                    <jats:sub>4<\/jats:sub>\n                    I\n                    <jats:sub>4<\/jats:sub>\n                    \/TiO\n                    <jats:sub>2<\/jats:sub>\n                    ) that achieves efficient and selective photocatalytic nitrate reduction to ammonia under mild conditions. The active site derived from an atomically precise Cu\n                    <jats:sub>4<\/jats:sub>\n                    I\n                    <jats:sub>4<\/jats:sub>\n                    Py\n                    <jats:sub>4<\/jats:sub>\n                    (Py\u00a0=\u00a0pyridine) nanocluster introduces sterically accessible copper sites with intrinsically unsaturated coordination and enhanced Lewis acidity for nitrate adsorption and activation. The iodide ligands in Cu\n                    <jats:sub>4<\/jats:sub>\n                    I\n                    <jats:sub>4<\/jats:sub>\n                    motif directly bonded to copper atoms are suggestive of promoting the generation of reactive hydrogen species (*H). The atomic\u2010scale proximity of copper and iodide sites facilitates efficient *H utilization in the multistep hydrogenation toward NH\n                    <jats:sub>3<\/jats:sub>\n                    . Consequently, Cu\n                    <jats:sub>4<\/jats:sub>\n                    I\n                    <jats:sub>4<\/jats:sub>\n                    \/TiO\n                    <jats:sub>2<\/jats:sub>\n                    delivers an ammonia generation rate of 26.8 mmol\u00b7g\n                    <jats:sub>cat<\/jats:sub>\n                    <jats:sup>\u22121<\/jats:sup>\n                    \u00b7h\n                    <jats:sup>\u22121<\/jats:sup>\n                    with good selectivity in a sacrificial\u2010reagent\u2010assisted photocatalytic nitrate reduction system. In situ characterizations and theoretical calculations support the plausible cooperative dual\u2010site mechanism, which synergistically ensures the deep hydrogenation of nitrate and its intermediates to ammonia. This work establishes an atomic\u2010level design paradigm for constructing multifunctional nanocluster catalysts that address the selectivity and efficiency challenges inherent to complex multiple proton\/electron\u2010involved reactions.\n                  <\/jats:p>","DOI":"10.1002\/anie.5529008","type":"journal-article","created":{"date-parts":[[2026,8,29]],"date-time":"2026-08-29T12:13:16Z","timestamp":1788005596000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Engineering Atomically Precise Cu\n                    <sub>4<\/sub>\n                    I\n                    <sub>4<\/sub>\n                    Nanoclusters With Integrated Adsorption and Hydrogenation Functions for Efficient Photocatalytic Nitrate\u2010to\u2010Ammonia Conversion"],"prefix":"10.1002","volume":"65","author":[{"given":"Wanting","family":"Zhang","sequence":"first","affiliation":[{"name":"International Joint Laboratory of Catalytic 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