3556 J. Phys. Chem. B 2000, 104, 3556-3562 Ammonia Adsorption on Keggin-Type Heteropolyacid Catalysts Explored by Density Functional Quantum Chemistry Calculations Billy B. Bardin, Robert J. Davis, and Matthew Neurock* Department of Chemical Engineering, UniVersity of Virginia, CharlottesVille, Virginia 22903-2442 ReceiVed: September 13, 1999; In Final Form: January 26, 2000 Density functional quantum chemical calculations have been used to compare the acid strengths of phosphotungstic and phosphomolybdic acids by computing the adsorption energy of ammonia on model clusters of each heteropolyacid. The adsorption of ammonia on a phosphotungstic acid cluster was stronger than the adsorption on a phosphomolybdic acid cluster. The predicted adsorption energies were near -150 and -106 kJ mol-1 for phosphotungstic and phosphomolybdic acid, respectively. This compares well with the experimental heats of ammonia sorption determined from microcalorimetry. An analysis of different adsorption modes of ammonia on phosphotungstic acid showed that bidentate adsorption of ammonia on the heteropolyacid clusters aided in proton transfer and yielded stronger adsorption energies than did a monodentate adsorption mode. In addition, we report the computed adsorption energies of pyridine on a heteropolyacid cluster. Introduction introduce the long-range effect of the zeolite cage on simulations of acid chemistry.13,14 During these studies, various molecules The drive to develop environmentally friendly chemical have been used to computationally explore the acid chemistry processes has motivated a significant increase in research of zeolites. Most common among these molecules are water, activities that encompass understanding and designing solid acid ammonia, and methanol.15 catalysts. These materials offer the unique opportunity to replace the corrosive liquid acids currently used in many chemical Herein, we have modeled the class of materials known as conversion steps to provide “greener” processes. The replace- heteropolyacids (HPAs) using density functional theory (DFT) ment of liquid acids with solid acid catalysts also simplifies quantum chemical calculations. Heteropolyacids prove to be downstream processing because no separation is needed to ideal from the computational standpoint because they have well- 16 recover the acid catalyst. Many materials have been used as defined local structures. In fact, the Keggin-type heteropoly- 17,18 solid acid catalysts including clays, zeolites, sulfated and acids have been examined using the extended Hu¨ckel theory. tungstated zirconia, and heteropolyacids.1 Each of these materi- Heteropolyacids are well-known strong acid catalysts, in both 19 als offers unique structural and chemical differences that can solution and solid forms, and catalyze paraffin skeletal 20-22 markedly influence the acid chemistry. Zeolites, for example, isomerization at low temperature. The most common HPA are excellent candidates for shape-selective chemistry because is the Keggin-type, but many other structures are also known. of their well-defined pore structure. These other structures, however, are thermally less stable and 23 Understanding the interaction of molecules with the acid sites therefore not as useful for acid catalysis. A schematic of the in these solid acid materials provides insight into the funda- primary structure of the Keggin-type HPA is shown in Figure x- mental chemistry. Discovering which technique provides the 1. The Keggin unit has the general formula QM12O40 , where best measure of solid acid strength has been a matter of dispute Q is the central atom (usually phosphorus or silicon), M is a for many years. As discussed in a recent paper,2 techniques such transition-metal atom (usually tungsten or molybdenum), and as temperature-programmed desorption, 1H NMR, microcalo- x is the charge on the primary structure. The Keggin unit is rimetry, and catalytic probe reactions have all been used as composed of a central tetrahedron surrounded by 12 transition- - alternatives to the controversial Hammett indicators to measure metal oxygen octahedra. The central tetrahedron is formed from solid acidity. Quantum chemical methods have also been used four oxygen atoms bonded to a central atom. Each transition- to model solid acidity. Two specific methods exist for modeling metal atom is bonded to six oxygen atoms to form the 12 acid strength. The first method involves calculating the proton octahedra on the outer-edge of the Keggin unit. Four types of affinity of the catalyst model as a theoretical measure of site oxygen atoms are found in the Keggin structure. These are the strength.3-5 However, there is no easy method to experimentally central oxygens, terminal oxygens, and two types of bridging determine solid acid proton affinity and, thus, no way to compare oxygens. Central oxygen atoms bridge the central atom with computed values to experimental results. The second method the transition-metal atoms. The terminal oxygens form a double that exists to probe acid site strength involves the calculation bond to a single transition-metal atom, whereas the bridging of adsorption energies of basic molecules such as ammonia and oxygen atoms form single bonds to two different transition- 16 pyridine on a catalyst model.6-11 These computed adsorption metal atoms. energies can be compared to the values determined from The acidity of heteropolyacids is Brønsted in nature. Keggin microcalorimetry.12 Both approaches have been used effectively units with a phosphorus as the central atom and a tungsten or to help characterize acidity in zeolites. Many small-model molybdenum as the transition metal atom will have a charge of clusters have been used to simulate the zeolite acid site, and in -3. To balance the negative charge on the Keggin structure, recent literature, embedded cluster models have been used to protons or cations are needed.23 The overall composition is then H3PM12O40, where M ) Mo or W. Heteropolyacids have not * To whom correspondence should be addressed. only a primary structure but also a secondary structure. The 10.1021/jp993227t CCC: $19.00 © 2000 American Chemical Society Published on Web 03/21/2000 Ammonia on Heteropolyacids J. Phys. Chem. B, Vol. 104, No. 15, 2000 3557 the calculations were performed in a manner whereby the entire structure including the cluster and the adsorbate were allowed to fully optimize to determine their corresponding energetics. The electronic structure for each cluster was determined by iterating on the density to solve the series of single-electron Kohn-Sham equations, thus providing a self-consistent solution. Analytical derivatives of the energy were computed at each SCF cycle and used to establish the relative changes in the nuclear coordinates for subsequent geometry optimization steps. All of the calculations were performed using the Vosko-Wilk-Nusair (VWN) exchange-correlation potential32 with Becke33,34 and Perdew35 nonlocal gradient corrections for the correlation and exchange energies, respectively. The gradient corrections were included in each iteration of the self-consistent field cycle. The density and energy of each SCF cycle were converged to within 1 × 10-3 and 1 × 10-5 au, respectively. The geometries were optimized to within 1 × 10-3 au. Triple-ú basis sets were Figure 1. The Keggin unit contains a central atom (phosphorus), employed for all atoms. The core electrons, up to and including addenda atoms (tungsten or molybdenum), and three types of oxygen the 4p, 5p, 2p, and 1s shells, were frozen for molybdenum, atoms (bridging, terminal, and central). tungsten, phosphorus, and oxygen atoms, respectively. Scalar relativistic corrections were explicitly included via the frozen secondary structure is determined by the number of waters of 19 core potentials. Relativistic corrections, along with geometry hydration found in the solid. Hydrogen bonds in a hydrated optimizations, were required for reliable predictions of structure sample help to maintain the secondary structure. In the hydrous and energetics. form, the protons are speculated to sit in the center of the secondary cavity between the water molecules, thus forming The clusters used in this paper were originally developed to + 24 aid in the calculation of the proton affinity of the Keggin-type an H5O2 species. In an anhydrous system, however, the 2 position of the proton is not as well-known. Lee et al. concluded heteropolyacids. They are labeled as monomer, dimer, trimer, from infrared spectroscopy that protons were most likely located tetramer, and Keggin unit, for which the value in the name on bridging oxygens,25 but others have suggested that the proton corresponds to the number of metal atoms found in the cluster. resides between two adjacent Keggin units hydrogen bonded For example, the monomer has one tungsten or molybdenum to terminal oxygens.26 In an earlier paper, we reported that the atom, whereas the dimer has two metal atoms. The clusters are most energetically favorable position for the proton in an small parts of the Keggin unit. The missing bonds at the edge isolated, anhydrous heteropolyacid was the bridging oxygen, of the cluster have been terminated with hydrogen atoms to as determined from calculated proton affinities.2 maintain neutrality. The Keggin unit is not a cluster, but instead, In this paper, we have used density functional quantum is the entire primary structure of the heteropolyacid. The clusters chemical calculations to model the interactions of ammonia with and structures