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A molecular-level understanding of how the electronic structure of metal center tunes the catalytic behaviors remains a grand challenge in heterogeneous catalysis. Herein, we report an unconventional kinetics strategy for bridging the microscopic metal electronic structure and the macroscopic steady-state rate for CO oxidation over Pt catalysts. X-ray absorption and photoelectron spectroscopy as well as electron paramagnetic resonance investigations unambiguously reveal the tunable Pt electronic structures with well-designed carbon support surface chemistry. Diminishing the electron density of Pt consolidates the CO-assisted O2 dissociation pathway via the O*-O-C*-O intermediate directly observed by isotopic labeling studies and rationalized by density-functional theory calculations. A combined steady-state isotopic transient kinetic and in situ electronic analyses identifies Pt charge as the kinetics indicators by being closely related to the frequency factor, site coverage, and activation energy. Further incorporation of catalyst structural parameters yields a novel model for quantifying the electronic effects and predicting the catalytic performance. These could serve as a benchmark of catalyst design by a comprehensive kinetics study at the molecular level. A molecular-level understanding of the electronic effects remains a grand challenge in heterogeneous catalysis. Here, the authors report an unconventional kinetics strategy for bridging the upscaling gap between the microscopic fingerprints of active sites and the macroscopic catalytic performance. [ABSTRACT FROM AUTHOR]

Enhanced electrochemical reduction of CO 2 to syngas on CuZnOCNT catalyst. • Copper doping on ZnO shifts the ECR activity towards CO formation closer to the top of the volcano. • The optimal amount of copper is around 20 at% for CO formation from electrochemical reduction of CO 2. • Higher amount of Cu doping leads to metallic Cu segregation, resulting in higher H 2 evolution activity. • The 14Cu86ZnO/CNT catalyst shows best performance in terms of syngas (1:1 ratio) production at -0.9 V, better than Ag foil. Electrochemical CO 2 reduction is a promising method for the production of CO 2 neutral fuels and chemicals from renewable electricity. ZnO supported on CNT is a low-cost electro catalyst that can produce syngas from CO 2 and H 2 O. A rational catalyst design strategy for further improvement of the ZnO/CNT catalyst is to dope with copper to strengthen the binding energy of the CO intermediate, which could improve the activity. In this work, a series of CuZnO/CNT catalysts with intimate Cu and Zn contact and various Cu loadings are prepared. By varying the copper content we show that the synergy of copper and zinc improves the activity for CO formation, and the optimal copper content is 20 at%. On hydrogen evolution, the addition of copper has a two-fold effect. This reaction is enhanced by the reduced ZnO particle size obtained when copper is added, but at similar particle sizes of ZnO, a suppression is observed with increasing copper content as CO evolution is enhanced. Stability tests showed that pure ZnO phase is more stable than metallic copper on ZnO. Compared with polycrystalline silver, the CuZnO/CNT catalysts are more active for syngas formation at a useful CO: H 2 composition. This work demonstrates that the viability of DFT based rational design of electrochemical CO 2 reduction catalyst. By varying CuZnO composition as well as crystallite size, one is able to tune the electrochemical reduction activity towards CO and H 2 , and therefore achieve desired syngas ratio. [ABSTRACT FROM AUTHOR]

• The reducibility and structural stability of LaMO 3 (M = Sc - Cu) are examined. • The first four LaMO 3 perovskites have very high oxygen vacancy formation energies. • The maximum possible oxygen deficiency in LaMO 3 (M = Mn - Ni) is 0.5. • LaCuO 3 can lose one lattice oxygen atom per formula unit before it is deactivated. Periodic density functional theory calculations have been performed to examine the effect of oxygen deficiency on the structural stability of Lanthanum-based perovskites (LaMO 3), where on-site Coulomb interactions have been addressed by an additional Hubbard-type term. Calculated results indicate that with the exception of LaFeO 3 , the oxygen vacancy formation energy (Δ E f o r m a t i o n , v a c ) of LaMO 3 (M = Sc - Cu) becomes less positive when moving across the first transition metal period. The first four LaMO 3 perovskites have very high oxygen vacancy formation energies and can hardly be reduced under mild conditions, while the other five perovskites exhibit a much greater reducibility. During the formation of the first oxygen vacancy in LaMO 3 (M = Mn - Cu), the nearest neighbor transition-metal cations serve as the primary acceptors of the electrons left behind. As oxygen atoms are further removed, square-based pyramidal and tetrahedral coordination geometries appear successively, and an abrupt increase in Δ E f o r m a t i o n , v a c is observed at a specific oxygen deficiency (δ), which defines the maximum possible δ in the perovskite structures. Under this definition, the M3+ cations (M = Mn - Ni) can be possibly reduced to M2+ while LaCuO 3 may lose at most one lattice oxygen atom per formula unit before it is deactivated. [ABSTRACT FROM AUTHOR]

[Display omitted] • Substitution of transition metals for Cr increases the acidity of the adjacent O. • Linear scaling relations are established to identify the PDH activity descriptor. • High propylene selectivity of the M 1 -Cr 2 O 3 catalysts is achieved. • Cu 1 -Cr 2 O 3 is predicted to be the best catalyst for PDH among the 13 doped Cr 2 O 3. The catalytic behavior of M 1 -Cr 2 O 3 (M = Mn-Cu, Ru-Ag, and Os-Au) in propane dehydrogenation (PDH) has been studied by employing microkinetic modeling combined with results from periodic DFT + U calculations. Calculated results indicate that most of the single atoms concerned can be stably present on the Cr 2 O 3 surface. The adsorption energy calculations and Bader charge analysis demonstrate that the acidity of the O sites adjacent to the M sites would be enhanced upon doping, which in turn strengthens the atomic H adsorption and the co-adsorption of various PDH species. The surface H formation energy is identified as the reactivity descriptor for PDH over the M 1 -Cr 2 O 3 catalysts, and a volcano curve of the PDH activity is obtained. By calculating the difference between the propylene dehydrogenation and desorption barriers, it is found that some M 1 -Cr 2 O 3 catalysts show improved selectivity towards propylene, as compared to Cr 2 O 3. Comparison between the formation barriers of H 2 and H 2 O reveals that single-atom doping has no apparent negative effect on the catalytic stability of the Cr 2 O 3 surface. The Cu 1 -Cr 2 O 3 catalyst is finally identified as the most promising catalyst for PDH among the 13 M 1 -Cr 2 O 3 catalyst candidates, considering the catalytic activity, selectivity, stability, and cost. [ABSTRACT FROM AUTHOR]

Abstract: Carbon nanofibers (CNFs) were synthesized by CO disproportionation on iron catalyst at CO concentration between 58.3% and 75.0%, H2 concentration between 8.3% and 25.0% and reaction temperature between 833 and 913K. The time-depending rate of CNFs growth as a function of time was determined by an on-line mass spectrometer and the morphologies of all CNFs products were observed by electronic microscopy. Not only the CNFs growth rate but also the morphology of the grown CNFs were shown to vary with the three operating variables. SEM and TEM images showed that the three-dimensional morphologies of the CNFs were twist, helical or straight and an interesting relationship between the maximal growth rate and the morphology was observed. When the growth rate was between 0.8 and 0.9mmol/(sgcat), the CNFs were twist. As the growth rate increased to 1.0mmol/(sgcat), more helical nanofibers appeared. Straight nanofibers were produced when the growth rate reached the level of 1.2mmol/(sgcat). Finally when the rate of CNFs growth was high at 1.8mmol/(sgcat), the absolute majority of the solid products was amorphous carbon coexisting with some short and thick nanofibers. Under different operating conditions, the crystal faces of the catalysts had different anisotropy properties for carbon deposition, thus producing CNFs with different morphologies. [Copyright &y& Elsevier]

Abstract: Dehydrogenation of propane (DHP) was studied over a series of xCr–SBA-15 and xCr–Al2O3 catalysts, prepared by incipient wetness impregnation, to gain a better understanding of the nature and distribution of Cr species and their catalytic function. To this end, the catalysts were characterized by N2-physisorption, X-ray diffraction (XRD), UV-Raman spectroscopy, scanning transmission electron microscopy–energy dispersive X-ray spectroscopy (STEM–EDXS) and X-ray absorption spectroscopy (XANES and EXAFS). All these characterization techniques indicate that, at ⩽1 wt% Cr, SBA-15 contains exclusively uniform distribution of chromium as isolated Cr(VI) species in tetrahedral () coordination, whilst on γ-Al2O3 a fraction of oligomers (including dimers) is present along with isolated species. At ⩾5 wt% Cr, SBA-15 is dominated by crystalline α-Cr2O3 particles, besides a fraction of isolated Cr(VI) species in coordination. Remarkably, γ-Al2O3 contains mainly oligomers with different degrees of nuclearity and a fraction of isolated species but no Cr2O3 particles. Among xCr–SBA-15 catalysts, those containing exclusively isolated Cr species (i.e., ⩽1 wt% Cr) exhibit higher activity and selectivity with respect to per mole of Cr than the catalyst dominated by crystalline α-Cr2O3 particles (⩾5 wt% Cr). The intrinsic activity of these isolated Cr species is higher than those observed on γ-Al2O3 (⩽1 wt% Cr). Interestingly, among xCr–Al2O3, the catalysts dominated by oligomeric species show the highest activity, indicating the important role of the species in the reaction. In situ XAS studies evidence that active Cr sites are apparently generated on-site during the reaction and that Cr is typically in (III) oxidation state. Based on ex situ and in situ characterization results and catalytic data, it appears that the activity of the Cr species is different in xCr–SBA-15 and xCr–Al2O3. For xCr–SBA-15, isolated Cr(III) sites with coordination number greater than four are more active, selective and stable than Cr sites on the surface of crystalline Cr2O3. In contrast, for xCr–Al2O3, oligomeric Cr species are more active and selective than the isolated Cr sites. [Copyright &y& Elsevier]