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@ARTICLE{Jung:636467,
author = {Jung, Hayoon and Cha, Gihoon and Kim, Hyesung and Will,
Johannes and Zhou, Xin and Bad'ura, Zdeněk and Zoppellaro,
Giorgio and Dobrota, Ana S. and Skorodumova, Natalia V. and
Pašti, Igor A. and Sarma, Bidyut Bikash and Schmidt, Jochen
and Spiecker, Erdmann and Breu, Josef and Schmuki, Patrik},
title = {{C}ation {V}acancies in {T}i‐{D}eficient {T}i{O}$_2$
{N}anosheets {E}nable {H}ighly {S}table {T}rapping of {P}t
{S}ingle {A}toms for {P}ersistent {P}hotocatalytic
{H}ydrogen {E}volution},
journal = {Small},
volume = {21},
number = {29},
issn = {1613-6810},
address = {Weinheim},
publisher = {Wiley-VCH},
reportid = {PUBDB-2025-03681},
pages = {2502428},
year = {2025},
abstract = {The stabilization of single-atom catalysts on semiconductor
substrates is pivotal for advancing photocatalysis. TiO$_2$,
a widely employed photocatalyst, typically stabilizes single
atoms at oxygen vacancies—sites that are accessible but
prone to agglomeration under illumination. Here, we
demonstrate that cation vacancies in Ti-deficient TiO$_2$
nanosheets provide highly stable anchoring sites for Pt
single atoms, enabling persistent photocatalytic hydrogen
evolution. Ultrathin TiO$_2$ nanosheets with intrinsic
Ti$^{4+}$ vacancies are synthesized via lepidocrocite-type
titanate delamination and Pt single atoms are selectively
trapped within these vacancies through a simple immersion
process. The resulting Pt-decorated nanosheets exhibit
superior photocatalytic hydrogen evolution performance,
outperforming both Pt nanoparticle-loaded nanosheets and
benchmarked Pt single-atom catalysts on P25. Crucially, Pt
atoms anchored at Ti$^{4+}$ vacancies display remarkable
resistance to light-induced agglomeration, a key limitation
of conventional single-atom photocatalysts. Density
functional theory calculations reveal that Pt incorporation
into Ti$^{4+}$ vacancies is highly thermodynamically
favorable and optimizes hydrogen adsorption energetics for
enhanced catalytic activity. This work highlights the
critical role of cation defect engineering in stabilizing
single-atom co-catalysts and advancing the efficiency and
durability of photocatalytic hydrogen evolution.},
cin = {DOOR ; HAS-User},
ddc = {620},
cid = {I:(DE-H253)HAS-User-20120731},
pnm = {6G3 - PETRA III (DESY) (POF4-6G3) / DFG project
G:(GEPRIS)431791331 - SFB 1452: Katalyse an flüssigen
Grenzflächen (CLINT) (431791331) / SAN4Fuel - Single atom
based nanohybrid photocatalyts for green fuels (101079384)},
pid = {G:(DE-HGF)POF4-6G3 / G:(GEPRIS)431791331 /
G:(EU-Grant)101079384},
experiment = {EXP:(DE-H253)P-P65-20150101},
typ = {PUB:(DE-HGF)16},
doi = {10.1002/smll.202502428},
url = {https://bib-pubdb1.desy.de/record/636467},
}