Different from isolated
metal atoms and large metal nanoparticles
(NPs), supported metal clusters (SMCs) possess distinct geometric
and electronic structures and thus exhibit enhanced activity and designated
selectivity in catalysis. So far, with the development in synthetic
methodologies and characterization techniques, SMCs with fine structures
could be constructed and well-defined at the atomic level. In addition,
based on computational modeling of SMCs, theoretical calculations
corroborated well with experimental results, providing in-depth insights
into the structure–property relationship for SMCs in catalysis.
In this Review, classic synthetic strategies and key characterization
techniques of SMCs are summarized. Subsequently, the applications
of SMCs in important catalytic reactions based on recent studies are
discussed, including aerobic oxidation, hydrogenation, dehydrogenation,
water–gas shift (WGS) reaction, and photocatalytic reactions.
In particular, the importance of the cluster size-effect and metal–support
interactions in determining the catalytic performance of SMCs is highlighted.
Lastly, challenges and prospects in SMCs’ catalysis are illustrated.
Indoleamine 2,3-dioxygenase (IDO-1) is emerging as an important new therapeutic target for the treatment of cancer, neurological disorders, and other diseases that are characterized by pathological tryptophan metabolism. However, only a few structural classes are known to be IDO-1 inhibitors. In this study, a natural compound tryptanthrin was discovered to be a novel potent IDO-1 inhibitor by screening of indole-based structures. Three series of 13 tryptanthrin derivatives were synthesized, and the structure-activity analysis was undertaken. The optimization led to the identification of 5c, which exhibited the inhibitory activity at a nanomolar level. In vitro 5c dramatically augmented the proliferation of T cells. When administered to Lewis lung cancer (LLC) tumor-bearing mice, 5c significantly inhibited IDO-1 activity and suppressed tumor growth. In addition, 5c reduced the numbers of Foxp3(+) regulatory T cells (Tregs), which are known to prevent the development of efficient antitumor immune responses.
Herein,
we report efficient single copper atom catalysts that consist
of dense atomic Cu sites dispersed on a three-dimensional carbon matrix
with highly enhanced mesoporous structures and improved active site
accessibility (Cu-SA/NC(meso)). The ratio of +1 to +2 oxidation state
of the Cu sites in the Cu-SA/NC(meso) catalysts can be controlled
by varying the urea content in the adsorption precursor, and the activity
for ORR increases with the addition of Cu1+ sites. The
optimal Cu1+-SA/NC(meso)-7 catalyst with highly accessible
Cu1+ sites exhibits superior ORR activity in alkaline media
with a half-wave potential (E
1/2) of 0.898
V vs RHE, significantly exceeding the commercial Pt/C, along with
high durability and enhanced methanol tolerance. Control experiments
and theoretical calculations demonstrate that the superior ORR catalytic
performance of Cu1+-SA/NC(meso)-7 catalyst is attributed
to the atomically dispersed Cu1+ sites in catalyzing the
reaction and the advantage of the introduced mesoporous structure
in enhancing the mass transport.
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