W. Nicholas Delgass

Size and Support Effects for the Water–Gas Shift Catalysis over Gold Nanoparticles Supported on Model Al2O3 and TiO2

The water-gas shift (WGS) reaction rate per total mole of Au under 7% CO, 8.5% CO(2), 22% H(2)O, and 37% H(2) at 1 atm for Au/Al(2)O(3) catalysts at 180 °C and Au/TiO(2) catalysts at 120 °C varies with the number average Au particle size (d) as d(-2.2±0.2) and d(-2.7±0.1), respectively. The use of nonporous and crystalline, model Al(2)O(3) and TiO(2) supports allowed the imaging of the active catalyst and enabled a precise determination of the Au particle size distribution and particle shape using transmission electron microscopy (TEM). Further, the apparent reaction orders and the stretching frequency of CO adsorbed on Au(0) (near 2100 cm(-1)) determined by diffuse reflectance infrared spectroscopy (DRIFTS) depend on d. Because of the changes in reaction rates, kinetics, and the CO stretching frequency with number average Au particle size, it is determined that the dominant active sites are the low coordinated corner Au sites, which are 3 and 7 times more active than the perimeter Au sites for Au/Al(2)O(3) and Au/TiO(2) catalysts, respectively, and 10 times more active for Au on TiO(2) versus Al(2)O(3). From operando Fourier transform infrared spectroscopy (FTIR) experiments, it is determined that the active Au sites are metallic in nature. In addition, Au/Al(2)O(3) catalysts have a higher apparent H(2)O order (0.63) and lower apparent activation energy (9 kJ mol(-1)) than Au/TiO(2) catalysts with apparent H(2)O order of -0.42 to -0.21 and activation energy of 45-60 kJ mol(-1) at near 120 °C. From these data, we conclude that the support directly participates by activating H(2)O molecules.

Sustainable fuel for the transportation sector

A hybrid hydrogen-carbon (H2CAR) process for the production of liquid hydrocarbon fuels is proposed wherein biomass is the carbon source and hydrogen is supplied from carbon-free energy. To implement this concept, a process has been designed to co-feed a biomass gasifier with H2 and CO2 recycled from the H2-CO to liquid conversion reactor. Modeling of this biomass to liquids process has identified several major advantages of the H2CAR process. (i) The land area needed to grow the biomass is <40% of that needed by other routes that solely use biomass to support the entire transportation sector. (ii) Whereas the literature estimates known processes to be able to produce ≈30% of the United States transportation fuel from the annual biomass of 1.366 billion tons, the H2CAR process shows the potential to supply the entire United States transportation sector from that quantity of biomass. (iii) The synthesized liquid provides H2 storage in an open loop system. (iv) Reduction to practice of the H2CAR route has the potential to provide the transportation sector for the foreseeable future, using the existing infrastructure. The rationale of using H2 in the H2CAR process is explained by the significantly higher annualized average solar energy conversion efficiency for hydrogen generation versus that for biomass growth. For coal to liquids, the advantage of H2CAR is that there is no additional CO2 release to the atmosphere due to the replacement of petroleum with coal, thus eliminating the need to sequester CO2.

A synergistic biorefinery based on catalytic conversion of lignin prior to cellulose starting from lignocellulosic biomass

Current biomass utilization processes do not make use of lignin beyond its heat value. Here we report on a bimetallic Zn/Pd/C catalyst that converts lignin in intact lignocellulosic biomass directly into two methoxyphenol products, leaving behind the carbohydrates as a solid residue. Genetically modified poplar enhanced in syringyl (S) monomer content yields only a single product, dihydroeugenol. Lignin-derived methoxyphenols can be deoxygenated further to propylcyclohexane. The leftover carbohydrate residue is hydrolyzed by cellulases to give glucose in 95% yield, which is comparable to lignin-free cellulose (solka floc). New conversion pathways to useful fuels and chemicals are proposed based on the efficient conversion of lignin into intact hydrocarbons.

Catalysis in a Cage: Condition-Dependent Speciation and Dynamics of Exchanged Cu Cations in SSZ-13 Zeolites

The relationships among the macroscopic compositional parameters of a Cu-exchanged SSZ-13 zeolite catalyst, the types and numbers of Cu active sites, and activity for the selective catalytic reduction (SCR) of NOx with NH3 are established through experimental interrogation and computational analysis of materials across the catalyst composition space. Density functional theory, stochastic models, and experimental characterizations demonstrate that within the synthesis protocols applied here and across Si:Al ratios, the volumetric density of six-membered-rings (6MR) containing two Al (2Al sites) is consistent with a random Al siting in the SSZ-13 lattice subject to Löwensteins rule. Further, exchanged Cu(II) ions first populate these 2Al sites before populating remaining unpaired, or 1Al, sites as Cu(II)OH. These sites are distinguished and enumerated ex situ through vibrational and X-ray absorption spectroscopies (XAS) and chemical titrations. In situ and operando XAS follow Cu oxidation state and coordination environment as a function of environmental conditions including low-temperature (473 K) SCR catalysis and are rationalized through first-principles thermodynamics and ab initio molecular dynamics. Experiment and theory together reveal that the Cu sites respond sensitively to exposure conditions, and in particular that Cu species are solvated and mobilized by NH3 under SCR conditions. While Cu sites are spectroscopically and chemically distinct away from these conditions, they exhibit similar turnover rates, apparent activation energies and apparent reaction orders at the SCR conditions, even on zeolite frameworks other than SSZ13.

Metallic Corner Atoms in Gold Clusters Supported on Rutile Are the Dominant Active Site during Water−Gas Shift Catalysis

Au/TiO(2) catalysts used in the water-gas shift (WGS) reaction at 120 °C, 7% CO, 22% H(2)O, 9% CO(2), and 37% H(2) had rates up to 0.1 moles of CO converted per mole of Au per second. However, the rate per mole of Au depends strongly on the Au particle size. The use of a nonporous, model support allowed for imaging of the active catalyst and a precise determination of the gold size distribution using transmission electron microscopy (TEM) because all the gold is exposed on the surface. A physical model of Au/TiO(2) is used to show that corner atoms with fewer than seven neighboring gold atoms are the dominant active sites. The number of corner sites does not vary as particle size increases above 1 nm, giving the surprising result that the rate per gold cluster is independent of size.

Isolation of the Copper Redox Steps in the Standard Selective Catalytic Reduction on Cu‐SSZ‐13

Operando X-ray absorption experiments and density functional theory (DFT) calculations are reported that elucidate the role of copper redox chemistry in the selective catalytic reduction (SCR) of NO over Cu-exchanged SSZ-13. Catalysts prepared to contain only isolated, exchanged Cu(II) ions evidence both Cu(II) and Cu(I) ions under standard SCR conditions at 473 K. Reactant cutoff experiments show that NO and NH3 together are necessary for Cu(II) reduction to Cu(I). DFT calculations show that NO-assisted NH3 dissociation is both energetically favorable and accounts for the observed Cu(II) reduction. The calculations predict in situ generation of Brønsted sites proximal to Cu(I) upon reduction, which we quantify in separate titration experiments. Both NO and O2 are necessary for oxidation of Cu(I) to Cu(II), which DFT suggests to occur by a NO2 intermediate. Reaction of Cu-bound NO2 with proximal NH4(+) completes the catalytic cycle. N2 is produced in both reduction and oxidation half-cycles.

A hybrid genetic algorithm for efficient parameter estimation of large kinetic models

Abstract The development of predictive models is a time consuming, knowledge intensive, iterative process where an approximate model is proposed to explain experimental data, the model parameters that best fit the data are determined and the model is subsequently refined to improve its predictive capabilities. Ascertaining the validity of the proposed model is based upon how thoroughly the parameter search has been conducted in the allowable range. The determination of the optimal model parameters is complicated by the complexity/non-linearity of the model, potentially large number of equations and parameters, poor quality of the data, and lack of tight bounds for the parameter ranges. In this paper, we will critically evaluate a hybrid search procedure that employs a genetic algorithm for identifying promising regions of the solution space followed by the use of an optimizer to search locally in the identified regions. It has been found that this procedure is capable of identifying solutions that are essentially equivalent to the global optimum reported by a state-of-the-art global optimizer but much faster. A 13 parameter model that results in 60 differential-algebraic equations for propane aromatization on a zeolite catalyst is proposed as a more challenging test case to validate this algorithm. This hybrid technique has been able to locate multiple solutions that are nearly as good with respect to the “sum of squares” error criterion, but imply significantly different physical situations.

Propane Aromatization over HZSM-5 and Ga/HZSM-5 Catalysts

The selective transformation of light alkanes to aromatics that are more valuable and versatile feedstocks for the chemical industry is one of the major challenges of catalytic chemistry. The complexity of the aromatization chemistry makes it difficult to unravel reaction mechanisms and, mechanistic information is largely developed from observed product distributions. This article reviews the current mechanistic understanding for the conversion of propane to aromatic compounds over HZSM‐5 and Ga/HZSM‐5 catalysts based on experimental as well as theoretical studies. Following a general discussion of acidity and confinement effects in these systems, this review focuses on understanding specific reactions occurring on Brønsted acid sites in HZSM‐5. Mechanistic details available from Density Functional Theory (DFT) calculations, as well as kinetic modeling efforts for various complex hydrocarbon systems are critically reviewed. A detailed, tabulated review of the literature compares the catalytic performance of gallium modified ZSM‐5 catalysts and subsequently the promotional effect of gallium as an additive is critically discussed in terms of the nature of the active sites, as well as the new reaction pathways introduced by gallium addition.

CO adsorption on pure and binary-alloy gold clusters: a quantum chemical study.

We performed density-functional theory analysis of nondissociative CO adsorption on 22 binary Au-alloy (Au(n)M(m)) clusters: n=0-3, m=0-3, and m+n=2 (dimers) or 3 (trimers), M=Cu/Ag/Pd/Pt. We report basis-set superposition error corrections to adsorption energies and include both internal energy of adsorption (DeltaU(ads)) and Gibbs free energy of adsorption (DeltaG(ads)) at standard conditions (298.15 K and 1 atm). We found onefold (atop) CO binding on all the clusters except Pd2 (twofold/bridged), Pt2 (twofold/bridged), and Pd3 (threefold). In agreement with the experimental results, we found that CO adsorption is thermodynamically favorable on pure Au/Cu clusters but not on pure Ag clusters and also observed the following adsorption affinity trend: Pd>Pt>Au>Cu>Ag. For alloy dimers we found the following patterns: Au2>M Au>M2 (M=Ag/Cu) and M2>M Au>Au2 (M=Pd/Pt). Alloying Ag/Cu dimers with (more reactive) Au enhanced adsorption and the opposite effect was observed for PdPt dimers. The Ag-Au, Cu-Au, and Pd-Au trimers followed the trends observed on dimers: Au3>M Au2>M2Au>M3 (M=Ag/Cu) and Pd3>Pd2Au>PdAu2>Au3. Interestingly, Pt-Au trimers reacted differently and alloying with Au systematically increased the adsorption affinity: PtAu2>Pt2Au>Pt3>Au3. A strikingly different behavior of Pt is also manifested by the triplet spin state and onefold (atop) binding in Pt3-CO which is in contradiction with the singlet spin state and threefold binding in Pd3-CO. We found a linear correlation between CO binding energy (BE) and elongation of the CO bond. For Ag-Au and Cu-Au clusters, the increase in CO BE (and elongation of the C-O bond which is probably due to the back donation) is accompanied by the decrease in the cluster-CO distance suggesting that the donation (from 5sigma highest occupied molecular orbital in CO to cluster lowest unoccupied molecular orbital) mechanism also contributes to the BE. For Pd-Au clusters, the cluster-CO distance (and CO bond length) increases with increase in the BE, suggesting that the donation mechanism may not be important for those clusters. No clear trend was observed for Pt-Au clusters.

Density functional theory investigation of gold cluster geometry and gas-phase reactivity with O2

We have conducted a density functional theory investigation into the gas-phase reactivity of small gold cluster ions in the interest of understanding gold cluster reactivity in several catalytic systems. Previously unreported geometries for Au9− and Au10− anions are obtained and reported from geometry optimizations. Predicted values of the vertical detachment energy match well with experiment, as does a rough simulation of its ultraviolet photoelectron spectrum—we found that comparison of predicted spectra with experimental data is a more sensitive analysis of geometry differences. Several binding sites for O2 with different energies are identified on Au10−, but we show that the strongest binding site and orientation is predicted by frontier orbital theory. In addition, weakly stable adsorbed states for O2 on the anion clusters Au9−, Au10−, and Au11− are predicted in agreement with frontier orbital theory. The calculated binding energies are consistent with the experimentally observed patterns in adsorpti...