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Figure S9), only with the binding energy of Pt changing into Pt
4f5/2 at 76.9 eV and Pt 4f7/2 at 73.5 eV. From the high-resolution
Pt 4f XPS, we found that the two oxidation states with binding
energy of Pt 4f5/2 at 77.6 eV and Pt 4f7/2 at 74.3 eV for Pt 4+ and
Pt 4f5/2 at 75.6 eV and Pt 4f7/2 at 72.3 eV for Pt 2+ changed into
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DOI: 10.1039/D0CC03325A
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one, indicating the valence state variation from two valence
4+
states into one. The high oxidation state of Pt
in the
composite solid (Pt/g-C3N4) experienced reduction as indicated
by reducing the 0.8 eV binding energy for Pt 4f7/2, while low
2+
oxidation state of Pt
appeared oxidation as shown by
increasing 1.2 eV binding energy, indicating the occurrence of
charge redistribution in the Pt/g-C3N4 during the photocatalytic
process. From the DFT calculation (Figure 2a), we found the Pt-
N coordinated bond acting as the electron transfer tunnel for
the Pt nanocluster and g-C3N4 in the composite solid.
In summary, we have explored a new solar-driven hole
oxidation approach enabled by a Pt/g-C3N4 composite solid
catalyst for photocatalytic anaerobic dehydrogenation of
alcohols to ketones with good conversion and high selectivity.
Under oxygen-free mild conditions, the transformation
sustainably proceeded and tolerated a broad range of
functional substrates including unactivated alcohols. The
reaction mechanism insights revealed a Pt-mediated hole
oxidation initiating the α-alcohol radical intermediate and two-
electron oxidation. This composite solid catalyst along with
heterogeneous solar-driven hole anaerobic oxidation would open
a sustainable approach towards the green and precise organic
synthetic chemistry.
This work was financially supported by the National Natural
Science Foundation of China (21961024, 21961025), Inner
Mongolia Natural Science Foundation (2018JQ05, 2019BS02008,
2019BS02007). Supported by Incentive Funding from Nano
Innovation Institute (NII) of Inner Mongolia University for
Nationalities (IMUN). Inner Mongolia Autonomous Region
Science & Technology Planning Project for Applied Technology
Research and Development (2019GG261), and Inner Mongolia
Autonomous Region Funding Project for Science & Technology
Achievement Transformation (CGZH2018156). Inner Mongolia
Autonomous Region Incentive Funding Guided Project for
Science & Technology Innovation (2016). Scientific Research
Projects of the Inner Mongolian Higher Educational System
(NJZZ20110). IMUN Doctoral Research Startup Fund Project
(BS445, BS437). IMUN Graduate Research Project (NMDSS1868,
NMDSS1937).
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Conflicts of interest
There are no conflicts to declare.
Notes and references
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