Strong metal–support
interaction (SMSI) has been regarded
as one of the most important concepts in heterogeneous catalysis,
which has been almost exclusively discussed in metal/oxide catalysts.
Here, we show that gold/molybdenum carbide (Au/MoC
x
) catalysts feature highly dispersed Au overlayers, strong
interfacial charge transfer between metal and support, and excellent
activity in the low-temperature water–gas shift reaction (LT-WGSR),
demonstrating the active SMSI state. Subsequent oxidation treatment
results in strong aggregation of Au nanoparticles, weak interfacial
electronic interaction, and poor LT-WGSR activity. The two interface
states can be transformed into each other by alternative carbonization
and oxidation treatments. This work reveals the active SMSI effect
in metal/carbide catalysts induced by carbonization, which opens a
new territory for this important concept.
Synergistic
effects have been discussed extensively in bimetallic
heterogeneous catalysis, but it remains unclear how the effects function
at the atomic scale. Here, we report a dual single-atom catalyst (DSAC)
Ir1Mo1/TiO2 displaying much greater
catalytic chemoselectivity (>96%, at 100% conversion) than comparable
single-atom catalysts (SACs) Ir1/TiO2 (38%,
at 87% conversion) and Mo1/TiO2 (no activity)
for the hydrogenation of 4-nitrostyrene (4-NS) to 4-vinylaniline (4-VA).
Activation of the TiO2-supported bimetallic carbonyl cluster
Ir2Mo2(CO)10(η5-C5H5)2 in an Ar atmosphere affords the
DSAC Ir1Mo1/TiO2. Characterization
of the dual single-atom structure confirms that it consists of well-dispersed
Ir single atoms (Ir1) and Mo single atoms (Mo1) on TiO2. Density functional theory studies reveal that
Ir1 sites effect H2 activation while Mo1 sites are responsible for 4-NS adsorption, with synergistic
cooperation between the two sets of single atoms contributing to the
better catalytic performance for the hydrogenation of 4-NS. This work
provides a deep understanding of synergistic effects in dual single-atom
catalysis.
Encapsulation of metal nanocatalysts by supportderived materials is well known as a classical strong metal−support interaction (SMSI) effect that occurs almost exclusively with active oxide supports and often blocks metal-catalyzed surface reactions. In the present work this classical SMSI process has been surprisingly observed between metal nanoparticles, e.g., Ni, Fe, Co, and Ru, and inert hexagonal boron nitride (h-BN) nanosheets. We find that weak oxidizing gases such as CO 2 and H 2 O induce the encapsulation of nickel (Ni) nanoparticles by ultrathin boron oxide (BO x ) overlayers derived from the h-BN support (Ni@BO x / h-BN) during the dry reforming of methane (DRM) reaction. Insitu surface characterization and theory calculations reveal that surface B−O and B−OH sites in the formed BO x encapsulation overlayers work synergistically with surface Ni sites to promote the DRM process rather than blocking the surface reactions.
The “Seven Pillars” of oxidation catalysis proposed by Robert K. Grasselli represent an early example of phenomenological descriptors in the field of heterogeneous catalysis. Major advances in the theoretical description of catalytic reactions have been achieved in recent years and new catalysts are predicted today by using computational methods. To tackle the immense complexity of high-performance systems in reactions where selectivity is a major issue, analysis of scientific data by artificial intelligence and data science provides new opportunities for achieving improved understanding. Modern data analytics require data of highest quality and sufficient diversity. Existing data, however, frequently do not comply with these constraints. Therefore, new concepts of data generation and management are needed. Herein we present a basic approach in defining best practice procedures of measuring consistent data sets in heterogeneous catalysis using “handbooks”. Selective oxidation of short-chain alkanes over mixed metal oxide catalysts was selected as an example.
Strong metal−support interaction (SMSI) has been widely recognized for platinum-group metals on reducible oxide supports. Herein we report that the catalytic activity of Ni catalyst in CO 2 methanation is significantly suppressed over conventional anatase (a-TiO 2 ) support due to the SMSI-induced formation of a titania overlayer around the Ni nanoparticles. Furthermore, CO is the only product . In contrast, the NH 3 -treatment and H 2 -treatment of the a-TiO 2 support enhance remarkably the activity of Ni, i.e., CO 2 conversion increases by 1 order of magnitude and CO 2 is hydrogenated almost exclusively to CH 4 . X-ray photoelectron spectroscopy (XPS), H 2 and CO chemisorption, and low temperature electron paramagnetic resonance (EPR) reveal that the enhanced CO 2 methanation activity may be related with the Ti 3+ species in the bulk that are generated by reduction treatment, which likely have altered the SMSI between Ni and a-TiO 2 support. This simple reduction treatment approach may be applicable to modulate the SMSI of other reducible oxide-supported metal catalysts.
Geometric or electronic confinement of guests inside nanoporous hosts promises to deliver unusual catalytic or opto-electronic functionality from existing materials but is challenging to obtain particularly using metastable hosts, such as metal–organic frameworks (MOFs). Reagents (e.g. precursor) may be too large for impregnation and synthesis conditions may also destroy the hosts. Here we use thermodynamic Pourbaix diagrams (favorable redox and pH conditions) to describe a general method for metal-compound guest synthesis by rationally selecting reaction agents and conditions. Specifically we demonstrate a MOF-confined RuO2 catalyst (RuO2@MOF-808-P) with exceptionally high catalytic CO oxidation below 150 °C as compared to the conventionally made SiO2-supported RuO2 (RuO2/SiO2). This can be caused by weaker interactions between CO/O and the MOF-encapsulated RuO2 surface thus avoiding adsorption-induced catalytic surface passivation. We further describe applications of the Pourbaix-enabled guest synthesis (PEGS) strategy with tutorial examples for the general synthesis of arbitrary guests (e.g. metals, oxides, hydroxides, sulfides).
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