Journal of the American Chemical Society
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higher activity than conventional transition metal nanopartiꢀ
cles on oxide or carbon supports. Mechanistic studies demonꢀ
strated that electron transfer from anionic electrons in
(4). (a) Jones, J.; Xiong, H.; DeLaRiva, A. T.; Peterson, E. J.; Pham,
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
H.; Challa, S. R.; Qi, G.; Oh, S.; Wiebenga, M. H.; Hernández,
X. I. P.; Wang, Y.; Datye, A. K. Science 2016, 353, 150; (b)
Liu, L.; Díaz, U.; Arenal, R.; Agostini, G.; Concepción, P.;
Corma, A. Nat. Mater. 2017, 16, 132; (c) Yan, H.; Cheng, H.;
Yi, H.; Lin, Y.; Yao, T.; Wang, C.; Li, J.; Wei, S.; Lu, J. J. Am.
Chem. Soc. 2015, 137, 10484.
LaCu0.67Si1.33 bulk promotes H dissociation on the highly
2
charged antiꢀbonding orbital of molecular hydrogen, which is
the rateꢀdetermining step of the investigated hydrogenation
reactions. The preferential adsorption of the reactant on the
catalyst surface through the oxygenꢀcontaining group leads to
excellent selectivity. LaCu0.67Si1.33 itself serves as a hydroꢀ
genation catalyst without the need for metal loading on the
surface; therefore, this study establishes transition metal based
LWF materials as new catalysts for such reactions, which
should simplify the entire preparation and reaction processes
for hydrogenation.
(5). (a) Dye, J. L. Science 1990, 247, 663; (b) Dye, J. L. Science
2003, 301, 607.
(6). (a) Toda, Y.; Hirayama, H.; Kuganathan, N.; Torrisi, A.; Suꢀ
shko, P. V.; Hosono, H. Nat. Commun. 2013, 4, 2378; (b) Choi,
S.; Kim, Y. J.; Kim, S. M.; Yang, J. W.; Kim, S. W.; Cho, E. J.
Nat. Commun. 2014, 5, 4881; (c) Kim, S. M.; Yoo, H. S.; Hoꢀ
sono, H.; Yang, J. W.; Kim, S. W. Sci. Rep. 2015, 5, 10366.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(
7). (a) Kitano, M.; Kanbara, S.; Inoue, Y.; Kuganathan, N.; Sushko,
P. V.; Yokoyama, T.; Hara, M.; Hosono, H. Nat. Commun.
2
015, 6, 6731; (b) Kanbara, S.; Kitano, M.; Inoue, Y.; Yokoꢀ
yama, T.; Hara, M.; Hosono, H. J. Am. Chem. Soc. 2015, 137,
4517; (c) Ye. T. N.; Li, J.; Kitano, M.; Sasase, M.; Hosono, H.
Supporting Information
1
Chem. Sci. 2016, 7, 5969; (d) Ye. T. N.; Li, J.; Kitano, M.; Hoꢀ
sono, H. Green. Chem. 2017, 19, 749.
The Supporting Information is available free of charge on the
ACS Publications website. brief description (file type, i.e., PDF)
brief description (file type, i.e., PDF)
(
(
8). Kitano, M.; Inoue, Y.; Yamazaki, Y.; Hayashi, F.; Kanbara, S.;
Matsuishi, S.; Yokoyama, T.; Kim, S.; Hara, M.; Hosono, H.
Nat. Chem. 2012, 4, 934.
9). Matsuishi, S. Toda, Y.; Miyakawa, M.; Hayashi, K.; Kamiya,
T.; Hirano, M.; Tanaka, I.; Hosono, H. Science 2003, 301, 626.
AUTHOR INFORMATION
(10). Kuganathan, N., Hosono, H., Shluger, A. L.; Sushko, P. V. J.
Am. Chem. Soc. 2014, 136, 2216.
Corresponding Author
eꢀmail: hosono@msl.titech.ac.jp
(
11). (a) Lu, Y. F.; Li, J.; Tada, T.; Toda, Y. Ueda, S.; Yokoyama, T.;
Kitano, M.; Hosono, H. J. Am. Chem. Soc. 2016, 138, 3970; (b)
Kitano, M.; Inoue, Y.; Ishikawa, H.; Yamagata, K.; Nakao, T.;
Tada, T.; Matsuishi, S.; Yokoyama, T.; Hara, M.; Hosono, H.
Chem. Sci. 2016, 7, 4036.
(12). (a) Studt, F.; AbildꢀPedersen, F.; Bligaard, T.; Sørensen, R. Z.;
Christensen, C. H.; Nørskov, J. K. Science 2008, 320, 1320; (b)
Armbrüster, M.; Kovnir, K.; Friedrich, M.; Teschner, D.;
Wowsnick, G.; Hahne, M.; Gille, P.; Szentmiklósi, L.; Feuerꢀ
bacher, M.; Heggen, M.; Girgsdies, F.; Rosenthal, D.; Schlögl,
R.; Grin, Y. Nat. Mater. 2012, 11, 690.
13). (a) Armbrüster, M.; Kovnir, K.; Behrens, M.; Teschner, D.;
Grin, Y.; Schlögl, R. J. Am. Chem. Soc. 2010, 132, 14745; (b)
Furukawa. S.; Komatsu, T. ACS Catal. 2017, 7, 735.
14). (a) Armbrüster, M.; Wowsnick, G.; Friedrich, M.; Heggen, M.;
CardosoꢀGil, R. J. Am. Chem. Soc. 2011, 133, 9112; (b) Feng,
Q.; Zhao, S.; Wang, Y.; Dong, J.; Chen, W.; He, D.; Wang, D.;
Yang, J.; Zhu, Y.; Zhu, H.; Gu, L.; Li, Z.; Liu, Y.; Yu, R.; Li, J.;
Li, Y. J. Am. Chem. Soc. 2017, 139, 7294; (c) Liu, Y.; Liu, X.;
Feng, Q.; He, D.; Zhang, L.; Lian, C.; Shen, R.; Zhao, G.; Ji, Y.;
Wang, D.; Zhou, G.; Li, Y. Adv. Mater. 2016, 28, 4747.
Author Contributions
†
These authors contributed equally.
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
(
This work was supported by funds from the Accelerated Innovaꢀ
tion Research Initiative Turning Top Science and Ideas into Highꢀ
Impact Values (ACCEL) program of the Japan Science and Techꢀ
(
nology Agency (JST), and
5H04183) from the Japan Society for the Promotion of Science
JSPS).
a Kakenhi GrantꢀinꢀAid (No.
1
(
REFERENCES
(
15). Gupta, S.; Suresh, K. G. J. Alloys Compd. 2015, 618, 562.
(
(
(
1). (a) Corma, A.; Serna, P. Science 2006, 313, 332; (b) Jagadeesh,
R. V.; Surkus, A. E.; Junge, H.; Pohl, M.ꢀM.; Radnik, J.; Rabeꢀ
ah, J.; Huan, H.; Schünemann, V.; Brückner, A.; Beller, M. Sciꢀ
ence 2013, 342, 1073.
(16). (a) Kresse, G.; Furthmüller, J. Comput. Mater. Sci. 1996, 6, 15;
b) Kresse, G.; Furthmüller, J. Phys. Rev. B 1996, 54, 11169.
17). Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996,
7, 3865.
(
(
(
7
2). (a) Zambelli, T.; Wintterlin, J.; Trost, J.; Ertl, G. Science 1996,
18). (a) Blöchl, P. E. Phys. Rev. B 1994, 50, 17953; (b) Kresse, G.;
Joubert, D. Phys. Rev. B 1999, 50, 1758.
2
9
2
73, 1688; (b) Farmer, J. A.; Campbell, C. T. Science 2010, 329,
33; (c) Li, X. H.; Wang, X.; Antonietti, M. Chem. Sci. 2012, 3,
170.
(19). Monkhorst, H. J.; Pack, J. D. Phys. Rev. B: Condens. Matter
976, 13, 5188.
1
3). (a) Liu, P.; Zhao, Y.; Qin, R.; Mo, S.; Chen, G.; Gu, L.;
Chevrier, D. M.; Zhang, P.; Guo, Q.; Zang, D.; Wu, B.; Fu, G.;
Zheng, N. Science 2016, 352, 797; (b) Qiao, B.; Wang, A.;
Yang, X.; Allard, L. F.; Jiang, Z.; Cui, Y.; Liu, J.; Li, J.; Zhang,
T. Nat. Chem. 2011, 3, 634; (c) Moliner, M.; Gabay, J. E.;
Kliewer, C. E.; Carr, R. T.; Guzman, J.; Casty, G. L.; Serna, P.;
Corma, A. J. Am. Chem. Soc. 2016, 138, 15743; (d) Ge, J.; He,
D.; Chen, W.; Ju, H.; Zhang, H.; Chao, T., Wang, X.; You, R.;
Lin, Y.; Wang, Y.; Zhu, J.; Li, H.; Xiao, B., Huang, W.; Wu, Y.;
Hong, X.; Li, Y. J. Am. Chem. Soc. 2016, 138, 13850; (e) Vilé,
G.; Albani, D.; Nachtegaal, M.; Chen, Z.; Dontsova, D.; Antoꢀ
nietti, M.; López, N.; PérezꢀRamírez, J. Angew. Chem. Int. Ed.
(
20). Tang, W.; Sanville, E.; Henkelman, G. J. Phys. Condens. Matꢀ
ter. 2009, 21, 084204.
21). (a) Lu, Y. F.; Tada, T.; Toda, Y. Ueda, S.; Wu, J.; Li, J.; Horiba,
K.; Kumigashira, H.; Zhang, Y.; Hosono, H. Phys. Rev. B 2017,
95, 125117; (b) Lee, K.; Kim, S. W.; Toda, Y.; Matsuishi, S.;
Hosono, H. Nature 2013, 494, 336.
22). Michaelson, H. B. J. Appl. Phys. 1977, 48, 4729.
23). Zhang, G.; Musgrave, C. B. J. Phys. Chem. A, 2007, 111, 1554.
24). (a) Gartland, P. O.; Berge, S. B.; Slagsvold, J. Phys. Rev. Lett.
(
(
(
(
1
972, 28, 738; (b) Drummond, T. J. SciTech Connect, 1999,
Available at https://www.osti.gov/scitech/biblio/3597.
(25). (a) Jagadeesh, R. V.; Surkus, A. E.; Junge, H.; Pohl, M.ꢀM.;
Radnik, J.; Rabeah, J.; Huan, H.; Schünemann, V.; Brückner,
2
015, 54, 11265.
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