Billo, T.T.BilloFu, F.-Y.F.-Y.FuRaghunath, P.P.RaghunathShown, I.I.ShownChen, W.-F.W.-F.ChenLien, H.-T.H.-T.LienShen, T.-H.T.-H.ShenLee, J.-F.J.-F.LeeChan, T.-S.T.-S.ChanHuang, K.-Y.K.-Y.HuangCHIH-I WULin, M.C.M.C.LinHwang, J.-S.J.-S.HwangLee, C.-H.C.-H.LeeLI-CHYONG CHENChen, K.-H.K.-H.Chen2020-06-182020-06-18201816136810https://scholars.lib.ntu.edu.tw/handle/123456789/503190https://www.scopus.com/inward/record.uri?eid=2-s2.0-85040313113&doi=10.1002%2fsmll.201702928&partnerID=40&md5=e0d3dc6fbb249c71c161ce5de4e646f7One of the key challenges in artificial photosynthesis is to design a photocatalyst that can bind and activate the CO2 molecule with the smallest possible activation energy and produce selective hydrocarbon products. In this contribution, a combined experimental and computational study on Ni-nanocluster loaded black TiO2 (Ni/TiO2[Vo]) with built-in dual active sites for selective photocatalytic CO2 conversion is reported. The findings reveal that the synergistic effects of deliberately induced Ni nanoclusters and oxygen vacancies provide (1) energetically stable CO2 binding sites with the lowest activation energy (0.08 eV), (2) highly reactive sites, (3) a fast electron transfer pathway, and (4) enhanced light harvesting by lowering the bandgap. The Ni/TiO2[Vo] photocatalyst has demonstrated highly selective and enhanced photocatalytic activity of more than 18 times higher solar fuel production than the commercial TiO2 (P-25). An insight into the mechanisms of interfacial charge transfer and product formation is explored. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheimartificial photosynthesis; black TiO2; photocatalytic CO2 reduction; solar fuels[SDGs]SDG7[SDGs]SDG13Activation energy; Binding sites; Bins; Carbon dioxide; Charge transfer; Chemical activation; Nanoclusters; Nickel; Nickel compounds; Oxygen vacancies; Photocatalysts; Photosynthesis; Product design; Titanium compounds; Titanium dioxide; Artificial photosynthesis; black TiO2; CO2 reduction; Computational studies; Fast electron transfer; Interfacial charge transfer; Photocatalytic activities; Solar fuels; Phosphorus compoundsjournal article10.1002/smll.201702928291347592-s2.0-85040313113