Jason A. Farmer

Ceria Maintains Smaller Metal Catalyst Particles by Strong Metal-Support Bonding

Keeping Nanoparticles Small Heterogeneous catalysts that consist of small metal nanoparticles absorbed on oxide supports can deactivate over time through a process called sintering. Elevated temperatures increase the rate of diffusion of metal atoms over the support, and larger, less reactive particles grow at the expense of smaller ones. Some supports that contain reducible metals, such as cerium oxide, tend to resist sintering better than oxides such as alumina. Farmer and Campbell (p. 933) present an analysis of previous calorimetry data for silver nanoparticles on magnesium oxides and cerium oxide surfaces and show that nanoparticles smaller than 1000 atoms are bound much more strongly to reduced cerium oxide. The energetic driving force for creating larger particles is quite low on these surfaces and increases the lifetime of smaller particles. The stability of cerium oxide surfaces allows deposited silver nanoparticles to maintain a small size distribution. The energies of silver (Ag) atoms in Ag nanoparticles supported on different cerium and magnesium oxide surfaces, determined from previous calorimetric measurements of metal adsorption energies, were analyzed with respect to particle size. Their stability was found to increase with particle size below 5000 atoms per particle. Silver nanoparticles of any given size below 1000 atoms had much higher stability (30 to 70 kilojoules per mole of silver atoms) on reduced CeO2(111) than on MgO(100). This effect is the result of the very large adhesion energy (~2.3 joules per square meter) of Ag nanoparticles to reduced CeO2(111), which we found to be a result of strong bonding to both defects and CeO2(111) terraces, apparently localized by lattice strain. These results explain the unusual sinter resistance of late transition metal catalysts when supported on ceria.

An improved single crystal adsorption calorimeter for determining gas adsorption and reaction energies on complex model catalysts

A new ultrahigh vacuum microcalorimeter for measuring heats of adsorption and adsorption-induced surface reactions on complex single crystal-based model surfaces is described. It has been specifically designed to study the interaction of gaseous molecules with well-defined model catalysts consisting of metal nanoparticles supported on single crystal surfaces or epitaxial thin oxide films grown on single crystals. The detection principle is based on the previously described measurement of the temperature rise upon adsorption of gaseous molecules by use of a pyroelectric polymer ribbon, which is brought into mechanical∕thermal contact with the back side of the thin single crystal. The instrument includes (i) a preparation chamber providing the required equipment to prepare supported model catalysts involving well-defined nanoparticles on clean single crystal surfaces and to characterize them using surface analysis techniques and in situ reflectivity measurements and (ii) the adsorption∕reaction chamber containing a molecular beam, a pyroelectric heat detector, and calibration tools for determining the absolute reactant fluxes and adsorption heats. The molecular beam is produced by a differentially pumped source based on a multichannel array capable of providing variable fluxes of both high and low vapor pressure gaseous molecules in the range of 0.005-1.5 × 10(15) molecules cm(-2) s(-1) and is modulated by means of the computer-controlled chopper with the shortest pulse length of 150 ms. The calorimetric measurements of adsorption and reaction heats can be performed in a broad temperature range from 100 to 300 K. A novel vibrational isolation method for the pyroelectric detector is introduced for the reduction of acoustic noise. The detector shows a pulse-to-pulse standard deviation ≤15 nJ when heat pulses in the range of 190-3600 nJ are applied to the sample surface with a chopped laser. Particularly for CO adsorption on Pt(111), the energy input of 15 nJ (or 120 nJ cm(-2)) corresponds to the detection limit for adsorption of less than 1.5 × 10(12) CO molecules cm(-2) or less than 0.1% of the monolayer coverage (with respect to the 1.5 × 10(15) surface Pt atoms cm(-2)). The absolute accuracy in energy is within ∼7%-9%. As a test of the new calorimeter, the adsorption heats of CO on Pt(111) at different temperatures were measured and compared to previously obtained calorimetric data at 300 K.

Improved pyroelectric detectors for single crystal adsorption calorimetry from 100 to 350 K.

The adsorption of atoms and molecules on single crystal surfaces allows one to produce well-characterized atomic, molecular, or dissociated adsorbates. Microcalorimetric measurement of the resulting adsorption energies, i.e., single crystal adsorption calorimetry, allows determination of the standard enthalpies of formation of these adsorbates. Methods are described for making an improved heat detector for such measurements, which greatly improves the signal-to-noise ratio, particularly at low temperatures (down to 100 K). The heat detector is an adaptation of a previously introduced design, based on a metallized pyroelectric polymer (beta-polyvinylidene fluoride), which is pressed against the back of a single crystal during measurement but removed during sample preparation and annealing. The improvement is achieved by selectively etching the metal coating of the polymer, thus reducing the pyro- and piezoelectric noise from all nonessential regions of the polymer. We, furthermore, describe how to achieve a better thermal contact between the sample and the pyroelectric polymer, without increasing the thermal mass of the detector, resulting in significantly improved sensitivities for both 1 and 127 microm thick samples. The result is a detector which, using 1 microm samples, is approximately 40 times more sensitive at 100 K than the traditional polymer-based detector, showing a pulse-to-pulse standard deviation in the heat of adsorption of just 1.3 kJ/mol with gas pulses containing only 1.1% of a monolayer onto Pt(111), for which 1 ML (monolayer) is 1.5x10(15) species/cm(2). For measurements at 300 K, where especially pyroelectric noise is likely of less concern, the new design improves the sensitivity 3.6-fold compared to the traditional detector. These improvements are furthermore used to propose a new detector design that is able to measure heats of adsorption on samples as thick as 127 microm with reasonable sensitivity.

Formation of the Calcium/Poly(3-Hexylthiophene) Interface: Structure and Energetics

The adsorption of Ca on poly(3-hexylthiophene) (P3HT) has been studied by adsorption microcalorimetry, atomic beam/surface scattering, X-ray photoelectron spectroscopy (XPS), low-energy He(+) ion scattering spectroscopy (LEIS), and first-principles calculations. The sticking probability of Ca on P3HT is initially 0.35 and increases to almost unity by 5 ML. A very high initial heat of adsorption in the first 0.02 ML (625-500 kJ/mol) is attributed to the reaction of Ca with defect sites or residual contamination. Between 0.1 and 0.5 ML, there is a high and nearly constant heat of adsorption of 405 kJ/mol, which we ascribe to Ca reacting with subsurface sulfur atoms from the thiophene rings of the polymer. This is supported by the absence of LEIS signal for Ca and the shift of the S 2p XPS binding energy by -2.8 eV for reacted S atoms. The heat of adsorption decreases above 0.6 ML coverage, reaching the sublimation enthalpy of Ca, 178 kJ/mol, by 4 ML. This is attributed to the formation of Ca nanoparticles and eventually a continuous solid Ca film, on top of the polymer. LEIS and XPS measurements, which show only a slow increase of the signals related to solid Ca, support this model. Incoming Ca atoms are subject to a kinetic competition between diffusing into the polymer to react with subsurface thiophene units versus forming or adding to three-dimensional Ca clusters on the surface. At approximately 1.6 ML Ca coverage, Ca atoms have similar probabilities for either process, with the former dominating at lower coverage. Ultimately about 1.6 ML of Ca (1.2 x 10(15) atoms/cm(2)) reacts with S atoms, corresponding to a reacted depth of approximately 3 nm, or nearly five monomer-unit layers. Density-functional theory calculations confirm that the heat of reaction and the shift of the S 2p signal are consistent with Ca abstracting S from the thiophene rings to form small CaS clusters.

Calcium adsorption on MgO(100): energetics, structure, and role of defects.

The adsorption of Ca on the MgO(100) surface at 300 K has been studied using microcalorimetry, in combination with LEED, AES, ISS, work function, sticking probability measurements, and density functional theory (DFT) calculations. The MgO(100) thin films (approximately 4 nm thick) were grown epitaxially on a 1 microm thick Mo(100) single-crystal. The sticking probability of Ca on MgO(100) at 300 K is unity. On the basis of AES and ISS measurements, it was determined that Ca grows mainly as 3D particles on the MgO(100) surface with a density of approximately 1 x 10(12) islands/cm2. Ca adsorbs initially at defect sites with a very high heat of adsorption (approximately 410 kJ/mol). DFT calculations attribute this high initial heat to Ca binding to kink sites (376 kJ/mol), step sites (205 kJ/mol), and lower concentrations of stronger binding sites. The heat of adsorption decreases rapidly with coverage, reaching a minimum of 162 kJ/mol at approximately 0.3 ML, where Ca is mainly adding to small 3D Ca clusters. Afterward, it increases to the value of bulk Ca heat of sublimation (178 kJ/mol) at approximately 1.2 ML, attributed to the increase in stability with increasing Ca particle size. A 1.0 eV decrease of the work function with Ca coverage from 0 to 0.3 ML indicates that Ca adsorbed at defects is cationic, in agreement with calculations showing that Ca donates electron density to the MgO. Light ion sputtering of the MgO(100) surface generates point defects, but these do not change the heat of adsorption versus coverage, implying that they do not nucleate Ca particles. Oxygen vacancies are a likely candidate; DFT calculations show that F and F+ center vacancies bind Ca more weakly than terrace sites. More extensive sputtering creates extended defects (such as steps and kinks) that adsorb Ca with heats of adsorption up to approximately 400 kJ/mol, similar to that at the intrinsic defect sites.

Interface Formation between Calcium and Electron-Irradiated Poly(3-hexylthiophene)

The adsorption of Ca on electron-irradiated poly(3-hexylthiophene) (P3HT) surfaces at 300 K (E(kin) = 100 eV) has been studied by adsorption microcalorimetry, atomic beam/surface scattering, X-ray photoelectron spectroscopy (XPS), and low-energy He(+) ion scattering spectroscopy (LEIS). The results are compared to previous studies of Ca adsorption on pristine P3HT. The major structural effect of electron irradiation is a substantial increase in the fraction of unsaturated carbon atoms, probably a result of electron-induced hydrogen abstraction from the hexyl chains and formation of new C=C double bonds. No loss of sulfur was observed. The combined XPS, LEIS, and calorimetry data indicate that the reaction and growth behavior of Ca on P3HT surfaces is not significantly affected by this electron damage, apart from an increased sticking probability at low coverages. The sticking probability of Ca on the irradiated P3HT is initially 0.63, compared to 0.36 on the pristine surface. It increases with coverage, approaching unity between 4 and 5 ML. The heat of adsorption stays nearly constant at 405 kJ/mol up to a coverage of 0.6 ML, which is ascribed to Ca diffusing below the surface and forming CaS clusters by abstraction of sulfur from the thiophene rings, based on XPS and LEIS data. The heat of adsorption then decreases gradually until it reaches the heat of sublimation of bulk Ca, 178 kJ/mol, by 4 ML; this is attributed to the formation of 3D Ca islands on top of the polymer, which eventually coalesce into a continuous Ca film by 11 ML. The heat of reaction versus coverage and the ultimate depth up to which the Ca atoms react with the polymer thiophene groups (approximately 3 nm) are nearly independent of electron damage, except for a difference in the heat of adsorption below 0.1 ML associated with defects or impurities. The increase in initial sticking probability caused by electron damage is attributed to stronger bonding of Ca adatoms to unsaturated versus saturated hydrocarbons. These very weakly held Ca adatoms are transient precursors to the two reactions which dominate the measured heat of adsorption (reaction with thiophene units and Ca cluster formation), but they can also desorb in this three-path kinetic competition. Mass spectrometer data show that these precursors have longer surface residence times on the electron-damaged surface.

Defect Sites and Their Distributions on MgO(100) by Li and Ca Adsorption Calorimetry

Chemical bonding to oxide surfaces is often dominated by surface defects, but their nature remains elusive. Calorimetric measurements of Ca and Li adsorption energies on MgO(100) and ion-damaged MgO(100), when combined with density functional theory (DFT) calculations and kinetic modeling, are shown to be a powerful way to assess the nature of the defect sites on oxide surfaces and their lateral distributions. While ion sputtering causes a strong increase in the initial adsorption energy for Li on MgO(100) at 300 K, the initial adsorption energy for Ca is independent of the extent of sputtering. This result and the measured coverage dependence of the adsorption energies of Ca and Li on MgO(100) surfaces with approximately 5, 12, and 25% defects were simulated with a kinetic model based on DFT input regarding site binding energies and adatom migration barriers. Reproducing the experimental results required models with distinct probability distributions of local defect concentrations for the differing extents of ion damage. A key difference between Li and Ca revealed by DFT and necessary to reproduce their differing adsorption energy versus ion damage measurements is the much greater tendency for a diffusing Li adatom to remain locked in place once it reaches a terrace site neighboring an occupied step or kink site, thus nucleating a 2D island on a terrace. In contrast, Ca adatoms thermally diffuse from such sites quickly, to seek out the remaining defect sites. The model also reproduces the measured Li and Ca film morphology seen by ion scattering spectroscopy.

Adsorption calorimetry during metal vapor deposition on single crystal surfaces: Increased flux, reduced optical radiation, and real-time flux and reflectivity measurements

Thin films of metals and other materials are often grown by physical vapor deposition. To understand such processes, it is desirable to measure the adsorption energy of the deposited species as the film grows, especially when grown on single crystal substrates where the structure of the adsorbed species, evolving interface, and thin film are more homogeneous and well-defined in structure. Our group previously described in this journal an adsorption calorimeter capable of such measurements on single-crystal surfaces under the clean conditions of ultrahigh vacuum [J. T. Stuckless, N. A. Frei, and C. T. Campbell, Rev. Sci. Instrum. 69, 2427 (1998)]. Here we describe several improvements to that original design that allow for heat measurements with ~18-fold smaller standard deviation, greater absolute accuracy in energy calibration, and, most importantly, measurements of the adsorption of lower vapor-pressure materials which would have previously been impossible. These improvements are accomplished by: (1) using an electron beam evaporator instead of a Knudsen cell to generate the metal vapor at the source of the pulsed atomic beam, (2) changing the atomic beam design to decrease the relative amount of optical radiation that accompanies evaporation, (3) adding an off-axis quartz crystal microbalance for real-time measurement of the flux of the atomic beam during calorimetry experiments, and (4) adding capabilities for in situ relative diffuse optical reflectivity determinations (necessary for heat signal calibration). These improvements are not limited to adsorption calorimetry during metal deposition, but also could be applied to better study film growth of other elements and even molecular adsorbates.