Elucidating the binding mode of carboxylate-containing ligands to gold nanoparticles (AuNPs) is crucial to understand their stabilizing role. A detailed picture of the three-dimensional structure and coordination modes of citrate, acetate, succinate and glutarate to AuNPs is obtained by C andNa solid-state NMR in combination with computational modelling and electron microscopy. The binding between the carboxylates and the AuNP surface is found to occur in three different modes. These three modes are simultaneously present at low citrate to gold ratios, while a monocarboxylate monodentate (1κO) mode is favoured at high citrate:gold ratios. The surface AuNP atoms are found to be predominantly in the zero oxidation state after citrate coordination, although trace amounts of Au are observed. Na NMR experiments show that Na ions are present near the gold surface, indicating that carboxylate binding occurs as a 2e L-type interaction for each oxygen atom involved. This approach has broad potential to probe the binding of a variety of ligands to metal nanoparticles.
Single atom catalysis (SAC) is a recent discipline of heterogeneous catalysis for which a single atom on a surface is able to carry out various catalytic reactions. A kind of revolution in heterogeneous catalysis by metals for which it was assumed that specific sites or defects of a nanoparticle were necessary to activate substrates in catalytic reactions. In another extreme of the spectrum, surface organometallic chemistry (SOMC), and, by extension, surface organometallic catalysis (SOMCat), have demonstrated that single atoms on a surface, but this time with specific ligands, could lead to a more predictive approach in heterogeneous catalysis. The predictive character of SOMCat was just the result of intuitive mechanisms derived from the elementary steps of molecular chemistry. This review article will compare the aspects of single atom catalysis and surface organometallic catalysis by considering several specific catalytic reactions, some of which exist for both fields, whereas others might see mutual overlap in the future. After a definition of both domains, a detailed approach of the methods, mostly modeling and spectroscopy, will be followed by a detailed analysis of catalytic reactions: hydrogenation, dehydrogenation, hydrogenolysis, oxidative dehydrogenation, alkane and cycloalkane metathesis, methane activation, metathetic oxidation, CO 2 activation to cyclic carbonates, imine metathesis, and selective catalytic reduction (SCR) reactions. A prospective resulting from present knowledge is showing the emergence of a new discipline from the overlap between the two areas.
Distinct photocatalytic performance was observed when Ta 3 N 5 was synthesized from commercially available Ta 2 O 5 or from Ta 2 O 5 prepared from TaCl 5 via the sol−gel route. With respect to photocatalytic O 2 evolution with Ag + as a sacrificial reagent, the Ta 3 N 5 produced from commercial Ta 2 O 5 exhibited higher activity than the Ta 3 N 5 produced via the sol−gel route. When the Ta 3 N 5 photocatalysts were decorated with Pt nanoparticles in a similar manner, the Ta 3 N 5 from the sol−gel route exhibited higher photocatalytic hydrogen evolution activity from a 10% aqueous methanol solution than Ta 3 N 5 prepared from commercial Ta 2 O 5 where no hydrogen can be detected. Detailed surface and bulk characterizations were conducted to obtain fundamental insight into the resulting photocatalytic activities. The characterization techniques, including XRD, elemental analysis, Raman spectroscopy, UV−vis spectroscopy, and surface-area measurements, revealed only negligible differences between these two photocatalysts. Our thorough characterization of the surface properties demonstrated that the very thin outermost layer of Ta 3 N 5 , with a thickness of a few nanometers, consists of either the reduced state of tantalum (TaN) or an amorphous phase. The extent of this surface layer was likely dependent on the nature of precursor oxide surfaces. DFT calculations based on partially oxidized Ta 3 N 4.83 O 0.17 and N deficient Ta 3 N 4.83 consisting of reduced Ta species well described the optoelectrochemical properties obtained from the experiments. Electrochemical and Mott−Schottky analyses demonstrated that the surface layer drastically affects the energetic picture at the semiconductor−electrolyte interface, which can consequently affect the photocatalytic performance. Chemical etching of the surface of Ta 3 N 5 particles to remove this surface layer unites the photocatalytic properties with the photocatalytic performance of these two materials. Mott−Schottky plots of these chemically etched Ta 3 N 5 materials exhibited similar characteristics. This result suggests that the surface layer (1−2 nm) determines the electrochemical interface, which explains the different photocatalytic performances of these two materials.
A lead-free and air-stable organohalide semiconductor exhibiting noteworthy optoelectronic properties is investigated. With improvements in thin film processing, this material is expected to yield good solar cell efficiency.
The direct transformation of CO2 into high-value-added hydrocarbons (i.e., olefins and aromatics) has the potential to make a decisive impact in our society. However, despite the efforts of the scientific community, no direct synthetic route exists today to synthesize olefins and aromatics from CO2 with high productivities and low undesired CO selectivity. Herein, we report the combination of a series of catalysts comprising potassium superoxide doped iron oxide and a highly acidic zeolite (ZSM-5 and MOR) that directly convert CO2 to either light olefins (in MOR) or aromatics (in ZSM-5) with high space–time yields (STYC2‑C4= = 11.4 mmol·g–1·h–1; STYAROM = 9.2 mmol·g–1·h–1) at CO selectivities as low as 12.8% and a CO2 conversion of 49.8% (reaction conditions: T = 375 °C, P = 30 bar, H2/CO2 = 3, and 5000 mL·g–1·h–1). Comprehensive solid-state nuclear magnetic resonance characterization of the zeolite component reveals that the key for the low CO selectivity is the formation of surface formate species on the zeolite framework. The remarkable difference in selectivity between the two zeolites is further rationalized by first-principles simulations, which show a difference in reactivity for crucial carbenium ion intermediates in MOR and ZSM-5.
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