Journal of the American Chemical Society
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two are due to quenching of the MLCT state by EtOH. The
(4) Goldemberg, J. Ethanol for a Sustainable Energy Future.
Science 2007, 315, 808-810.
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TA spectrum of Cu (H
PO
4
)
@Ru-UiO showed similar long-
x
y
time components but different short time constants of 75 fs,
1.2 ps, and 9.1 ps, indicating fast electron transfer between
Cu and [Ru (BPY) (BPYDC)] (Figure 4e, Figure S21). This
2
(5) Farrell, A. E.; Plevin, R. J.; Turner, B. T.; Jones, A. D.;
O'Hare, M.; Kammen, D. M. Ethanol Can Contribute to
Energy and Environmental Goals. Science 2006, 311, 506-508.
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Irabien, A. Copper-Based Metal–Organic Porous Materials
for CO2 Electrocatalytic Reduction to Alcohols.
ChemSusChem 2017, 10, 1100-1109.
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C. W.; Herman, R. G. Higher alcohol and oxygenate synthesis
over cesium-doped copper/zinc oxide catalysts. J. Catal. 1989,
116, 195-221.
II
II
*
assignment is supported by increased absorption below 530
nm and decreased absorption above 550 nm due to
I
III
generation of Cu and Ru at 0.5 ps (Figure S22). On the
other hand, TA spectrum of Cu-NPs@Ru-UiO showed
distinct dynamics with time constants of 116 fs, 34 ps, 3.6 ns,
and > 10 ns. The TA spectrum at 0.5 ps is similar to inversed
plasmonic absorption of Cu NPs (Figure 4e, Figure S21),
suggesting electron transfer from the Cu NP to
0
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0
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0
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9
0
II
*
I
[Ru (BPY)
2
(BPYDC)] to generate Cu .
(8) Zhao, N.; Xu, R.; Wei, W.; Sun, Y. Cu/Mn/ZrO2 catalyst
for alcohol synthesis by Fischer-Tropsch modified elements.
React. Kinet. Catal. Lett. 2002, 75, 297-304.
In summary, we have used low-intensity light to in situ
II
activate a Cu (H
x
PO
4
)
y
@Ru-UiO catalyst for selective CO
EtOH. Under light illumination,
2
(
9) Liu, Y.; Murata, K.; Inaba, M.; Takahara, I.; Okabe, K.
hydrogenation to
(BPYDC)] undergoes SET to both Cu and Cu to
generate Cu for catalytic EtOH production. In contrast, the
II
*
II
0
Mixed alcohols synthesis from syngas over Cs- and Ni-
modified Cu/CeO2 catalysts. Fuel 2013, 104, 62-69.
[Ru (BPY)
2
I
0
(10) Rungtaweevoranit, B.; Baek, J.; Araujo, J. R.; Archanjo, B.
S.; Choi, K. M.; Yaghi, O. M.; Somorjai, G. A. Copper
Nanocrystals Encapsulated in Zr-based Metal–Organic
Frameworks for Highly Selective CO2 Hydrogenation to
Methanol. Nano. Lett. 2016, 16, 7645-7649.
(11) Cao, A.; Liu, G.; Wang, L.; Liu, J.; Yue, Y.; Zhang, L.; Liu,
Y. Growing layered double hydroxides on CNTs and their
catalytic performance for higher alcohol synthesis from
syngas. J. Mater. Sci. 2016, 51, 5216-5231.
same catalyst forms Cu NPs as the active species for MeOH
2
production from CO hydrogenation in the dark. This work
suggests new opportunities in using light to stabilize metal
centers of an intermediate oxidation state for selective
chemical transformations.
ASSOCIATED CONTENT
(
12) Liu, Y.; Murata, K.; Inaba, M.; Takahara, I.; Okabe, K.
Supporting Information
Synthesis of mixed alcohols from syngas over Cs-modified
Cu/Ce1-xZrxO2 catalysts. J. Jpn. Pet. Inst. 2010, 53, 153-159.
(13) An, B.; Li, Z.; Song, Y.; Zhang, J.; Zeng, L.; Wang, C.; Lin,
Internet
at
Synthesis
and
characterization of MOFs, photocatalytic CO
2
reduction
W. Cooperative copper centres in
a
metal–organic
procedures, details of ligand synthesis and NMR spectrum.
framework for selective conversion of CO2 to ethanol. Nature
Catal. 2019, 2, 709-717.
AUTHOR INFORMATION
Corresponding Author
(
14) Prasad, D. R.; Ferraudi, G. Photochemistry of transition-
metal phthalocyanines. Monophotonic and sequential
biphotonic photochemical processes of copper(II) tetrakis(N-
octadecylsulfamoyl)phthalocyanine in nonaqueous media.
Inorg. Chem. 1982, 21, 2967-2971.
*chengwangxmu@xmu.edu.cn
Notes
(
15) Tasdelen, M. A.; Ciftci, M.; Yagci, Y. Visible Light-
The authors declare no competing financial interests.
Induced Atom Transfer Radical Polymerization. Macromol.
Chem. Phys. 2012, 213, 1391-1396.
ACKNOWLEDGMENT
(
16) Kuo, C.-H.; Tang, Y.; Chou, L.-Y.; Sneed, B. T.; Brodsky,
We acknowledge funding support from Ministry of Science
and Technology of the P. R. China (2016YFA0200702) and the
National Natural Science Foundation (21671162, 21721001).
C. N.; Zhao, Z.; Tsung, C.-K. Yolk–Shell Nanocrystal@ZIF-8
Nanostructures for Gas-Phase Heterogeneous Catalysis with
Selectivity Control. J. Am. Chem. Soc. 2012, 134, 14345-14348.
(
17) Wang, L.; Agnew, D. W.; Yu, X.; Figueroa, J. S.; Cohen, S.
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