Identification and characterization of catalytic active sites are the prerequisites for an atomic-level understanding of the catalytic mechanism and rational design of high-performance heterogeneous catalysts. Indirect evidence in recent reports suggests that platinum (Pt) single atoms are exceptionally active catalytic sites. We demonstrate that infrared spectroscopy can be a fast and convenient characterization method with which to directly distinguish and quantify Pt single atoms from nanoparticles. In addition, we directly observe that only Pt nanoparticles show activity for carbon monoxide (CO) oxidation and water-gas shift at low temperatures, whereas Pt single atoms behave as spectators. The lack of catalytic activity of Pt single atoms can be partly attributed to the strong binding of CO molecules.
Developing supported single-site catalysts is an important goal in heterogeneous catalysis since the well-defined active sites afford opportunities for detailed mechanistic studies, thereby facilitating the design of improved catalysts. We present herein a method for installing Ni ions uniformly and precisely on the node of a Zr-based metal-organic framework (MOF), NU-1000, in high density and large quantity (denoted as Ni-AIM) using atomic layer deposition (ALD) in a MOF (AIM). Ni-AIM is demonstrated to be an efficient gas-phase hydrogenation catalyst upon activation. The structure of the active sites in Ni-AIM is proposed, revealing its single-site nature. More importantly, due to the organic linker used to construct the MOF support, the Ni ions stay isolated throughout the hydrogenation catalysis, in accord with its long-term stability. A quantum chemical characterization of the catalyst and the catalytic process complements the experimental results. With validation of computational modeling protocols, we further targeted ethylene oligomerization catalysis by Ni-AIM guided by theoretical prediction. Given the generality of the AIM methodology, this emerging class of materials should prove ripe for the discovery of new catalysts for the transformation of volatile substrates.
This study reports the highly selective (more than 95%) dehydrogenation of propane to propylene as well as the reverse hydrogenation reaction by silica-supported single-site Zn(II) catalyst. The catalyst is thermally stable at dehydrogenation temperature (550 °C and above), and catalytic byproducts are small. In situ UV-resonance Raman, XANES, and EXAFS spectra reveal that tetrahedrally coordinated Zn(II) ions are chemisorbed into the strained three-membered siloxane rings on the amorphous silica surface. Under reaction conditions, the Zn(II) ion loses one Zn–O bond, resulting in a coordinatively unsaturated, 3-coordinate active center. The infrared spectrum of adsorbed pyridine indicates that these are Lewis acid sites. Theoretical calculations based on hybrid density functional theory suggest that the catalyst activates H–H and C–H bonds by a nonredox (metal) mechanism consisting of heterolytic cleavage of C–H bonds, in contrast with the homolytic mechanisms such as oxidative addition/reductive elimination pathways. The computed minority catalytic pathway consists of undesired C–C bond cleavage at Zn(II) site, follows a slightly different mechanism, and has a significantly higher activation energy barrier. These mechanisms are consistent with the high olefin selectivity observed for single-site Zn(II) on SiO2.
Zr-based metal–organic frameworks (MOFs) have been shown to be excellent catalyst supports in heterogeneous catalysis due to their exceptional stability. Additionally, their crystalline nature affords the opportunity for molecular level characterization of both the support and the catalytically active site, facilitating mechanistic investigations of the catalytic process. We describe herein the installation of Co(II) ions to the Zr6 nodes of the mesoporous MOF, NU-1000, via two distinct routes, namely, solvothermal deposition in a MOF (SIM) and atomic layer deposition in a MOF (AIM), denoted as Co-SIM+NU-1000 and Co-AIM+NU-1000, respectively. The location of the deposited Co species in the two materials is determined via difference envelope density (DED) analysis. Upon activation in a flow of O2 at 230 °C, both materials catalyze the oxidative dehydrogenation (ODH) of propane to propene under mild conditions. Catalytic activity as well as propene selectivity of these two catalysts, however, is different under the same experimental conditions due to differences in the Co species generated in these two materials upon activation as observed by in situ X-ray absorption spectroscopy. A potential reaction mechanism for the propane ODH process catalyzed by Co-SIM+NU-1000 is proposed, yielding a low activation energy barrier which is in accord with the observed catalytic activity at low temperature.
Nanostructured carbides are refractory materials with high surface areas that could be used as alternatives to the oxide materials that are widely used as support materials for heterogeneous catalysts. Carbides are also catalytically active for a variety of reactions, offering additional opportunities to tune the overall performance of the catalyst. In this paper we describe the synthesis of molybdenum carbide supported platinum (Pt/Mo(2)C) catalysts and their rates for the water gas shift reaction. The synthesis method allowed interaction of the metal precursor with the native, unpassivated support. The resulting materials possessed very high WGS rates and atypical Pt particle morphologies. Under differential conditions, rates for these catalysts were higher than those for the most active oxide-supported Pt catalysts and a commercial Cu-Zn-Al catalyst. Experimental and computational results suggested that active sites on the Pt/Mo(2)C catalysts were located on the perimeter of the Pt particles and that strong interactions between Pt and the Mo(2)C surface gave rise to raft-like particles.
We report the synthesis, characterization, and catalytic performance for gas phase propane dehydrogenation of single site Co 2+ ions supported on silica. Spectroscopic characterization by resonance Raman, electron paramagnetic resonance, and X-ray near edge and extended absorption fine structure revealed that tetrahedrally coordinated Co 2+ ions are chemisorbed into the trisiloxane rings on the surface of amorphous silica. In situ XAS shows that Co is not oxidized by air nor reduced by hydrogen even at 650°C. For catalytic propane dehydrogenation, single site Co 2+ /SiO 2 exhibits selectivities > 95% at 550°C and > 90% at 650°C with stable activity over 24 h. Calculations with hybrid density functional theory support a non-redox mechanism for activation of C-H and H-H bonds by Co 2+ similar to that previously reported for single site Zn 2+ /SiO 2 .
Pd–Ag alloy catalysts with very dilute amounts of Pd were synthesized. EXAFS results demonstrated that when the concentration of Pd was as low as 0.01 wt %, Pd was completely dispersed as isolated single atoms in Ag nanoparticles. The activity for the hydrogenation of acrolein was improved by the presence of these isolated Pd atoms due to the creation of sites with lower activation energy for H2 dissociation. In addition, for the same particle size, the 0.01% Pd/8% Ag alloy nanoparticles exhibited higher selectivity than their monometallic counterparts, suggesting that the Pd atom may act as a site for the favorable bonding of the acrolein molecule for facile hydrogenation of the aldehyde functionality.
The OH groups on the Zr-based nodes of ultrastable UiO-66 can be metallated with V V ions in a facile fashion to give the derivative VUiO-66. This metallated MOF exhibits high stability over a broad temperature range and displays high selectivity for benzene under low-conversion conditions in the vapor-phase oxidative dehydrogenation of cyclohexene (activation energy ∼110 kJ/mol). The integrity of the MOF is maintained after catalysis as determined by PXRD, ICP-AES, and SEM.
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