Catalysis: new perspectives from surface science

One-sixth of the value of all goods manufactured in the United States involves catalytic processes. However, in spite of this dramatic economic impact, little is known about this broad subject at the molecular level. In the last two decades a variety of techniques have been developed for studying at the atomic level the structure, composition, and chemical bonding at surfaces. These techniques have been used to study adsorption and reaction on metal single crystals in an ultrahigh vacuum environment or to analyze catalysts before and after reaction. An important new development has been the coupling of an apparatus for the measurement of reaction kinetics at elevated pressures with an ultrahigh vacuum system for surface analysis. This approach has demonstrated that metal single crystals can be used to successfully model many important catalytic reactions and has established a direct link between the results of ultrahigh vacuum surface measurements and the chemistry that occurs under typical catalytic-processing conditions.     

Structure of the Reduced TiO2(110) Surface Determined by Scanning Tunneling Microscopy

The scanning tunneling microscope has been used to image a reduced TiO(2)(110) surface in ultrahigh vacuum. Structural units with periodicities rangng from 21 to 3.4 angstroms have been clearly imaged, demonstrating that atomic resolution imaging of an ionic, wide band gap (3.2 electron volts) semiconductor is possible. The observed surface structures can be explained by a model involving ordered arrangements of two-dimensional defects known as crystallographic shear planes and indicate that the topography of nonstoichiometric oxide surfaces can be complex.     

Intercalated clay catalysts

Recent advances in the intercalation of metal complex cations in smectite clay minerals are leading to the development of new classes of selective heterogeneous catalysts. The selectivity of both metal-catalyzed and proton-catalyzed chemical conversions in clay intercalates can often be regulated by controlling surface chemical equilibria, interlamellar swelling, or reactant pair proximity in the interlayer regions. Also, the intercalation of polynuclear hydroxy metal cations and metal cluster cations in smectites affords new pillared clay catalysts with pore sizes that can be made larger than those of conventional zeolite catalysts.     

Heterogeneous atmospheric reactions: sulfuric Acid aerosols as tropospheric sinks

The collisional reaction probabilities of several atmospheric species on bulk sulfuric acid surfaces indicate that heterogeneous processes may be important in tropospheric chemistry.     

Electron- and photon-stimulated desorption: probes of structure and bonding at surfaces

Techniques for analyzing the structure and composition of solid surfaces with electron and photon beams often cause radiation damage in samples. Damage-producing processes compete with information-producing events during measurements, and beam damage can be a serious perturbation in quantitative surface analysis. There are, however, substantial benefits of electron- and photonstimulated damage processes for studying molecules adsorbed on surfaces. Direct information about the geometric structure of surface molecules can be obtained from measurements of the angular distributions of ions released by electron- or photon-stimulated desorption. The directions of ion emission are determined by the orientation of the surface bonds that are ruptured by beam irradiation. Moreover, photon-stimulated desorption studies that make use of synchrotron radiation reveal the fundamental electronic excitations that lead to bondbreaking processes at surfaces. These measurements provide new insights into radiation-damage processes in areas as diverse as x-ray optics and semiconductor electronics.     

Mass spectrometry sampling under ambient conditions with desorption electrospray ionization

A new method of desorption ionization is described and applied to the ionization of various compounds, including peptides and proteins present on metal, polymer, and mineral surfaces. Desorption electrospray ionization (DESI) is carried out by directing electrosprayed charged droplets and ions of solvent onto the surface to be analyzed. The impact of the charged particles on the surface produces gaseous ions of material originally present on the surface. The resulting mass spectra are similar to normal ESI mass spectra in that they show mainly singly or multiply charged molecular ions of the analytes. The DESI phenomenon was observed both in the case of conductive and insulator surfaces and for compounds ranging from nonpolar small molecules such as lycopene, the alkaloid coniceine, and small drugs, through polar compounds such as peptides and proteins. Changes in the solution that is sprayed can be used to selectively ionize particular compounds, including those in biological matrices. In vivo analysis is demonstrated.     

Direct observation of chemical bond dynamics on surfaces

The dynamics of chemisorbed species as they swing to-and-fro on their adsorption sites may be directly observed with electron-stimulated desorption. The observation of the thermal disorder in adsorbate chemical bond directions, through studies of the thermal excitation of librational modes, allows one to visualize the potential energy surfaces controlling the structure and dynamics of adsorbates on single crystal metal and semiconductor surfaces. This information may be useful in understanding surface diffusion as well as the spatial aspects of surface chemical reactions.     

Small-diameter silicon nanowire surfaces

Small-diameter (1 to 7 nanometers) silicon nanowires (SiNWs) were prepared, and their surfaces were removed of oxide and terminated with hydrogen by a hydrofluoric acid dip. Scanning tunneling microscopy (STM) of these SiNWs, performed both in air and in ultrahigh vacuum, revealed atomically resolved images that can be interpreted as hydrogen-terminated Si (111)-(1 x 1) and Si (001)-(1 x 1) surfaces corresponding to SiH3 on Si (111) and SiH2 on Si (001), respectively. These hydrogen-terminated SiNW surfaces seem to be more oxidation-resistant than regular silicon wafer surfaces, because atomically resolved STM images of SiNWs were obtained in air after several days' exposure to the ambient environment. Scanning tunneling spectroscopy measurements were performed on the oxide-removed SiNWs and were used to evaluate the electronic energy gaps. The energy gaps were found to increase with decreasing SiNW diameter from 1.1 electron volts for 7 nanometers to 3.5 electron volts for 1.3 nanometers, in agreement with previous theoretical predictions.     

真空处理对青霉菌的抑制及吸湿性能影响研究

接种青霉菌橡胶木在温度15 ℃、绝对真空度7 mmHg(即933 Pa)下,分别处理0、12、24、36、48、60、72 h。经霉菌稀释计数观察青霉菌数量,傅里叶变换红外光谱、热重分析仪和动态水蒸气吸附分析仪分析橡胶木表面化学结构、热稳定性与吸湿解吸性能。结果表明,真空处理可明显抑制青霉菌生长,处理60 h,青霉菌几乎完全被杀死;接菌橡胶木与真空处理接菌橡胶木,其纤维素、半纤维素和木质素均有所降解,橡胶木表面亲水基团增加,表面亲水性增强,且后者易炭化,热稳定性能稍有降低;侵染青霉菌的橡胶木吸湿与解吸性能有所增大,真空处理后更趋明显。该研究可为真空处理抑制木材霉菌生长技术提供理论参考。     

Atomic-scale desorption through electronic and vibrational excitation mechanisms

The scanning tunneling microscope has been used to desorb hydrogen from hydrogen-terminated silicon (100) surfaces. As a result of control of the dose of incident electrons, a countable number of desorption sites can be created and the yield and cross section are thereby obtained. Two distinct desorption mechanisms are observed: (i) direct electronic excitation of the Si-H bond by field-emitted electrons and (ii) an atomic resolution mechanism that involves multiple-vibrational excitation by tunneling electrons at low applied voltages. This vibrational heating effect offers significant potential for controlling surface reactions involving adsorbed individual atoms and molecules.     

A microscopic basis for the global appearance of energy landscapes

It is shown that the appearance of a multidimensional potential energy surface, or potential energy landscape, can be related to the form of the interatomic or intermolecular potential. Catastrophe theory enables us to describe how the geometry of the surface changes with parameters in the potential, and provides universal scaling relations that explain, for example, the asymmetric reaction profiles observed for systems bound by long-range forces. The principal result is an unexpected connection between barrier heights, path lengths, and vibrational frequencies, with applications to a wide variety of problems in chemical physics, ranging from Hammond's postulate in organic chemistry, to the relaxation dynamics of complex systems such as glasses and biomolecules.     

Atomic Force Microscope Studies of Fullerene Films: Highly Stable C60 fcc (311) Free Surfaces

Atomic force microscopy and x-ray diffractometry were used to study 1500 A-thick films of pure C(60) grown by sublimation in ultrahigh vacuum onto a CaF(2) (111) substrate. Topographs of the films did not reveal the expected close-packed structures, but they showed instead large regions that correspond to a face-centered cubic (311) surface and distortions of this surface. The open (311) structure may have a relatively low free energy because the low packing density contributes to a high entropy of the exposed surface.     

The Chemistry of Bulk Hydrogen: Reaction of Hydrogen Embedded in Nickel with Adsorbed CH3

Studies in heterogeneous catalysis have long speculated on or have provided indirect evidence for the role of hydrogen embedded in the catalyst bulk as a primary reactant. This report describes experiments carried out under single-collision conditions that document the distinctive reactivity of hydrogen embedded in the bulk of the metal catalyst. Specifically, the bulk H atom is shown to be the reactive species in the hydrogenation of CH(3) adsorbed on Ni(111) to form CH(4), while the H atoms bound to the surface were unreactive. These results unambiguously demonstrate the importance of bulk species to heterogeneous catalytic chemistry.     

Chemisorption of water at high temperatures on kaolinite: effect on dehydroxylation

The dehydroxylation reaction of kaolinite in a vacuum at 425 degrees C is halted by introducing a water vapor pressure of 47 mm-Hg, and is resumed when the vacuum is reestablished. The sample gains weight corresponding to an approximately monomotecular layer of water on the kaolinite surface. At the temperatures and vapor pressures involved, the sorption is considered to be a chemisorption process.     

Quantum States and atomic structure of silicon surfaces

The electronic and geometric structures of surfaces are closely related to each other. Conventional surface science techniques can study one or the other, but not both at the same time. Recent developments in scanning tunneling microscopy have made it possible to study simultaneously the electronic and geometric structure of Si(111) and Si(001) surfaces. Surface states can be atomically resolved in space and energy; thus the electronic structure of single atoms on surfaces can be studied in detail. The various surface states observed on silicon surfaces are found to derive from different atomic-scale features in the surface geometric structure. Scanning tunneling microscopy has now bridged the gap between electronic and geometric structure, providing a unique opportunity to obtain a better understanding of many surface processes at the atomic level.     

Growth of SiO2 at room temperature with the use of catalyzed sequential half-reactions

Films of silicon dioxide (SiO2) were deposited at room temperature by means of catalyzed binary reaction sequence chemistry. The binary reaction SiCl4 + 2H2O --> SiO2 + 4HCl was separated into SiCl4 and H2O half-reactions, and the half-reactions were then performed in an ABAB ellipsis sequence and catalyzed with pyridine. The pyridine catalyst lowered the deposition temperature from >600 to 300 kelvin and reduced the reactant flux required for complete reactions from approximately 10(9) to approximately 10(4) Langmuirs. Growth rates of approximately 2.1 angstroms per AB reaction cycle were obtained at room temperature for reactant pressures of 15 millitorr and 60-second exposure times with 200 millitorr of pyridine. This catalytic technique may be general and should facilitate the chemical vapor deposition of other oxide and nitride materials.     

Rocks from the mantle transition zone: majorite-bearing xenoliths from malaita, southwest pacific

Rocks containing high-pressure mineral assemblages derived from the mantle transition zone between depths of about 400 and 670 kilometers occur as xenoliths and megacrysts on the island of Malaita in the southwest Pacific on the Ontong Java Plateau. Observed ultrahigh pressure mineral chemistries include majorite, calcium- and magnesium-perovskite, aluminous silicate phases, and microdiamond. Based on an empirical barometer, majoritic garnets in these xenoliths record pressures of up to 22 gigapascal. The occurrence of material with perovskite chemistry and several enigmatic aluminous phases indicates pressures of up to 27 gigapascal. Samples were brought to the surface at about 34 million years ago by potassic ultramafic magmas, which evidently originated in the lower mantle.     

Surface-directed liquid flow inside microchannels

Self-assembled monolayer chemistry was used in combination with either multistream laminar flow or photolithography to pattern surface free energies inside microchannel networks. Aqueous liquids introduced into these patterned channels are confined to the hydrophilic pathways, provided the pressure is maintained below a critical value. The maximum pressure is determined by the surface free energy of the liquid, the advancing contact angle of the liquid on the hydrophobic regions, and the channel depth. Surface-directed liquid flow was used to create pressure-sensitive switches inside channel networks. The ability to confine liquid flow inside microchannels with only two physical walls is expected to be useful in applications where a large gas-liquid interface is critical, as demonstrated here by a gas-liquid reaction.     

几种粘粒矿物和土壤表面吸附态磷的解吸 Ⅰ吸附和解吸滞后的机理(英文)

研究了可变电荷粘粒矿物和矿物学性质不同的代表性土壤对磷酸根的等温解吸特性。结果表明磷酸根的解吸等温线一般都滞后于吸附等温线。滞后的程度以铁、铝氧化物最大;含较多铁和铝氧化物的酸性土壤其次;高岭石、蒙脱石和中性、石灰性土壤较小。磷酸根的解吸率一般都随着吸附饱和度的增加而增加,但在各吸附饱和度下,解吸率都明显低于吸附磷的同位素(磷)交换率。在恒定pH和离子强度下,解吸主要涉及结合能较低的吸附态磷。可变电荷表面紧结合态吸附磷在同样条件下是极难解吸的,从而引起磷酸根吸附和解吸不可逆转。此外,吸附态磷还可能通过次生化学反应而转化成不溶性磷酸盐化合物,对这种形态磷就不能通过简单的水液平衡而发生可逆性的解吸作用,而必须加以某种化学处理(例如适当酸化或用有机物质)。     

几种粘粒矿物和土壤表面吸附态磷的解吸(英文)

几种重要粘粒矿物和我国代表性土壤表面吸附态磷的解吸随pH的变化可以归纳为三种不同的曲线类型.铁铝氧化物和蒙脱石表面磷的解吸在pH4.0到10.0范围内随pH升高而增加,pH6.0到7.5以上增加更快.高岭石和以可变电荷为主的酸性红黄壤的磷解吸—pH曲线呈现“U”型特征,其解吸最低值的pH高岭石为6.5,红黄壤类样品都在4.8左右.中性和石灰性土壤磷解吸在pH酸侧类似碳酸钙的情况,即解吸随pH升高线性下降,但在pH高于6.0～7.5以上时,解吸又趋于稳定,甚至增加.pH对磷吸附和解吸的影响在本质上是一样的,但方向相反.高岭石和红黄壤等具可变电荷表面的样品的磷解吸最小值pH范围恰好都落在各样品吸附磷前后的两个PZC值之间.上述结果表明可变电荷矿物和土壤吸附态磷的解吸在很大程度上受表面电荷特性 制约.pH影响此类样品磷解吸的机理主要是改变了表面电位.至于中性和石灰性土壤,磷的释放在pH酸侧主要受磷酸钙溶解作用支配;而在较高pH条件下,粘粒矿物表面吸附磷的解吸仍然是重要的.