Hydrothermal ethanol conversion on Ag,Cu, Au/TiO2

The effect UV irradiation and silver, copper, and gold ions (M ^z+) supported on titania (anatase) have on the activity of M/TiO₂ samples in ethanol conversion at 150–400°C is examined. After UV irradiation, the yields of acetaldehyde and ethylene increase for TiO₂ and Ag/TiO₂ samples, while the activity of Cu²⁺/TiO₂ decreases. The activation energy of ethanol dehydration declines in the order TiO₂ > Au³⁺ > Cu²⁺ > Ag⁺ and correlates linearly with a reduction in the radius of M ^z+ in crystal. The number of acidic sites on a M/TiO₂ surface titrated via pyridine adsorption grows upon the introduction of M. Unlike Cu²⁺/TiO₂, these sites are not activated after the irradiation of TiO₂, Ag⁺/TiO₂, and Au³⁺/TiO₂. According to IR spectral data on adsorbed pyridine, all samples contain Lewis and Brönsted acidic sites.     

Heterogeneity of surface colour centres on alkaline earth metal oxides as revealed through EPR/ENDOR spectroscopy

A variety of surface anion vacancies, or point defects, are created by high‐temperature activation of a series of polycrystalline alkaline earth metal oxides (MgO, CaO and SrO). Subsequent UV irradiation of the activated oxide under a hydrogen atmosphere results in the generation of surface colour centres [F_S⁺(H)], by electron trapping at these anion vacancies. The paramagnetic properties of these colour centres were studied by EPR and ENDOR spectroscopy. ¹H ENDOR spectroscopy revealed that a well defined heterogeneity of trapped electron species exists on each oxide surface, as characterized by the different superhyperfine couplings between the trapped electron and the nearby proton of the F_S⁺ (H) centre. On MgO and CaO two dominant F_S⁺ (H) centres were identified (labelled sites I and II) whereas on SrO three F_S⁺ (H) species were found (sites I, II and III). The possible surface sites responsible for electron stabilization are discussed, and include a 3C corner mono‐vacancy, a 4C mono‐vacancy and an anion–cation di‐vacancy. The results indicate that regardless of the oxide used, a common degree of morphological similarities exists on each oxide. Copyright © 2002 John Wiley & Sons, Ltd.     

Uncovering selective and active Ga surface sites in gallia–alumina mixed-oxide propane dehydrogenation catalysts by dynamic nuclear polarization surface enhanced NMR spectroscopy

Gallia–alumina (Ga,Al)₂O_3(x : y) spinel-type solid solution nanoparticle catalysts for propane dehydrogenation (PDH) were prepared with four nominal Ga : Al atomic ratios (1 : 6, 1 : 3, 3 : 1, 1 : 0) using a colloidal synthesis approach. The structure, coordination environment and distribution of Ga and Al sites in these materials were investigated by X-ray diffraction, X-ray absorption spectroscopy (Ga K-edge) as well as ²⁷Al and ⁷¹Ga solid state nuclear magnetic resonance. The surface acidity (Lewis or Brønsted) was probed using infrared spectroscopy with pyridine and 2,6-dimethylpyridine probe molecules, complemented by element-specific insights (Ga or Al) from dynamic nuclear polarization surface enhanced cross-polarization magic angle spinning ¹⁵N{²⁷Al} and ¹⁵N{⁷¹Ga} J coupling mediated heteronuclear multiple quantum correlation NMR experiments using ¹⁵N-labelled pyridine as a probe molecule. The latter approach provides unique insights into the nature and relative strength of the surface acid sites as it allows to distinguish contributions from Al and Ga sites to the overall surface acidity of mixed (Ga,Al)₂O₃ oxides. Notably, we demonstrate that (Ga,Al)₂O₃ catalysts with a high Al content show a greater relative abundance of four-coordinated Ga sites and a greater relative fraction of weak/medium Ga-based surface Lewis acid sites, which correlates with superior propene selectivity, Ga-based activity, and stability in PDH (due to lower coking). In contrast, (Ga,Al)₂O₃ catalysts with a lower Al content feature a higher fraction of six-coordinated Ga sites, as well as more abundant Ga-based strong surface Lewis acid sites, which deactivate through coking. Overall, the results show that the relative abundance and strength of Ga-based surface Lewis acid sites can be tuned by optimizing the bulk Ga : Al atomic ratio, thus providing an effective measure for a rational control of the catalyst performance.

Coordination geometry and Lewis acidity of Ga and Al (bulk and surface) sites in mixed oxide gallia–alumina nanoparticles is correlated with the performance in propane dehydrogenation.     

Properties of surface acid sites of ZrO2 and SO4ZrO2-based systems studied by diffuse-reflectance Fourier-transform IR spectroscopy: adsorption of acetonitrile-d3

The properties of acid sites of ZrO₂ and SO₄/ZrO₂-based systems modified by metal ions were studied by DRIFT spectroscopy using acetonitrile-d₃ as a probe molecule. In the case of ZrO₂. CD₃CN interacts with the Lewis acid sites (LAS) with moderate strength. Adsorption on the Brönsted acid sites (BAS) is very weak, which indicates the absence of strong BAS on the surface of ZrO₂. Modification of the surface by SO₄ groups results in the appearance of a new type of BAS that are capable of adsorbing CD₃CN in the polycoordinated form,i.e., stronger complexes with the adsorbate. Addition of metal ions (Fe, Ga, Zn, or Co) leads to the formation of a new type of LAS connected with Fe³⁺, Ga³⁺, Zn²⁺, and Co²⁺ promoter ions.     

CuMgAlO_x复合氧化物催化甲醇乙醇Guerbet反应:M~(2+)/Al~(3+)比的影响

以类水滑石为前驱体,通过调控M~(2+)/Al~(3+)比制备了系列具有不同表面性质的MgAlO_x(MA)和CuMgAlO_x(CMA)催化剂,并分别应用于甲醛乙醛缩合反应(甲醇乙醇Guerbet反应的第二步反应)和甲醇乙醇Guerbet反应。采用NH_3/CO_2-TPD、XPS、H_2-TPR和H_2-TPD技术对催化剂表面酸碱性以及铜物种的性质进行了表征。结果表明,甲醇乙醇Guerbet反应性能与催化剂表面Cu~0比表面积和中强碱数目有关,提高Cu~0比表面积有利于甲醇乙醇脱氢生成甲醛和乙醛,增强中强碱数目能促进甲醛乙醛缩合反应。     

Structure of the CO bond on supported Pd particles: influence of size and surface state

We have investigated the surface of supported palladium particles by static secondary ion mass spectrometry (SSIMS). Pd particles were grown in situ on alumi na (oxide layer and sapphire surfaces) and stabilized by heating treatment. The particle size, density and crystallographic structure were determined in previous studies by transmission electron microscopy and diffraction (TEM and TED). Various ionic species are detected by SSIMS analysis which makes it possible to characterize the CO absorbed layer: Pd _n CO⁺ (n=1, 2) for molecular adsorption and Pd _n C⁺ for CO dissociation. The size dependence of the bonding state of CO (linear, bridge, ...) was monitored by: PdCO⁺/σ _n Pd _n CO⁺ signal ratio over various size particles (mean diameter in the 2–9 nm range). Investigations were performed as a function of CO coverage (adsorption at room temperature) and also under CO dissociation conditions: heating under CO atmosphere or CO+O₂ (catalysis). The data analysis shows that on clean Pd particles smaller than 3 nm the CO molecules give rise mainly to PdCO⁺ species. We have interpreted this result by the adsorption of CO on two palladium atoms, the carbon end being tightly bonded to a low coordination Pd atom and the oxygen end weakly bonded to a neighbour Pd atom. These couples of Pd atoms form the specific sites for CO dissociation, the density of which depends on the roughness of the particle surface.     

Highly Porous Zirconium Aryldiphosphonates and Their Conversion to Strong Bronsted Acids

Porous inorganic-organic hybrids have been prepared by the reaction of 4,4′-biphenylbis(phosphonic acid) with Zr(IV) in organic solvents. The resultant products consist of α-zirconium phosphate-type layers crosslinked by biphenyl pillars. By using an excess of Zr in the synthesis, surface areas of ∼400 m²/g have been obtained and the pores can be controlled to be the micro-type with diameters of 10-20 Å and a relatively narrow pore size distribution. The aromatic rings are readily sulfonated by SO₃ under pressure to produce very strong Bronsted acid catalysts. An NMR procedure, utilizing the shift of the carbonyl carbon of acetone-2-¹³C sorbed onto the sulfonated products, indicated an acid strength for the Bronsted acid sites equal to that of 100% sulfuric acid. Unpillared Zr(O₃PC₆H₄SO₃H)₂ has a somewhat lower acid strength, but still has a higher acid strength than zeolites HX and HY. The particles of this layered acid exfoliate in water and light-scattering data show that they are in 5 nm size range. They also exhibit high proton conductivity as solid membranes. These sulfonated materials have a potential as strong acid catalysts for a variety of reactions at a low temperature.     

The in situ study of surface species and structures of oxide-derived copper catalysts for electrochemical CO2 reduction

Oxide-derived copper (OD-Cu) has been discovered to be an effective catalyst for the electroreduction of CO₂ to C2+ products. The structure of OD-Cu and its surface species during the reaction process are interesting topics, which have not yet been clearly discussed. Herein, in situ surface-enhanced Raman spectroscopy (SERS), operando X-ray absorption spectroscopy (XAS), and ¹⁸O isotope labeling experiments were employed to investigate the surface species and structures of OD-Cu catalysts during CO₂ electroreduction. It was found that the OD-Cu catalysts were reduced to metallic Cu(0) in the reaction. CuO_x species existed on the catalyst surfaces during the CO₂RR, which resulted from the adsorption of preliminary intermediates (such as *CO₂ and *OCO⁻) on Cu instead of on the active sites of the catalyst. It was also found that abundant interfaces can be produced on OD-Cu, which can provide heterogeneous CO adsorption sites (strong binding sites and weak binding sites), leading to outstanding performance for obtaining C2+ products. The Faradaic efficiency (FE) for C2+ products reached as high as 83.8% with a current density of 341.5 mA cm⁻² at −0.9 V vs. RHE.

CuO_x species were shown to exist on OD-Cu during the CO₂RR, which resulted from the adsorption of preliminary intermediates (such as *CO₂ and *OCO⁻) on Cu instead of on the active sites of the catalyst.     

Successful location of tin dopant cations on surface sites of anatase-type TiO2 crystallites evidenced by 119Sn Mössbauer spectroscopic probe and XPS techniques

The present study provides the first experimental evidence for the stabilization of tin dopant cations immediately on the surface of an oxide having a tetragonal structure. ¹¹⁹Sn Mössbauer spectra of the dopant, introduced by air annealing into the bulk of anatase microcrystals, showed that it was located, in the tetravalent state, in somewhat distorted octahedral sites of a unique type. On the contrary, the reduced tin species, formed upon subsequent hydrogen annealing the Sn⁴⁺-doped samples, are found to occupy different sites being characterized by two sets of the isomer shift δ and quadrupole splitting ΔE_Q values (δ_I = 3.25 mm s⁻¹, ΔE_QI = 1.75 mm s⁻¹; and δ_II = 2.85 mm s⁻¹, ΔE_QII = 1.71 mm s⁻¹). Either of them implies both the divalent state of tin atoms and their presence at low-coordination sites that can be assigned to the surface of crystallites. Mössbauer spectra of Sn^4+←2+ daughter ions, formed upon contact with air of Sn²⁺, consist of a symmetrically broadened peak characterized by only slightly different average values of both the isomer shift (<δ> = 0.07 mm s⁻¹) and quadrupole splitting (<ΔE_Q> = 0.50 mm s⁻¹), as compared to the δ and ΔE_Q values for the bulk-located Sn⁴⁺. However, considerable broadening of Sn^4+←2+ doublet components (Γ = 0.97 mm s⁻¹) allows one to suggest that these secondary formed ions remain distributed over the non equivalent sites inherited from their Sn²⁺ precursors. The occurrence of Sn^4+←2+ at surface sites is independently proven by XPS measurements that revealed a greater than 10-fold enrichment with tin of 3–5 nm thick surface layers.     

XPS studies on the gold oxide surface layer formation

The initial stage of gold oxide layer formation on the gold electrode surface was investigated in 0.5 M H₂SO₄. X-ray photoelectron spectroscopy (XPS) spectra of pure gold and the anodically polarized gold electrode surface were compared quantitatively. It was found that gold anodic polarization in the E range from ∼1.3 to 2.1 V causes increase in intensity of the XPS spectra at an electron binding energy ε_b=85.9 eV for gold and at ε_b=530 eV for oxygen. These ε_b values correspond to Au³⁺ and O²⁻ oxidation states in hydrous or anhydrous gold oxide. The larger the amount of the anodically formed surface substance the higher is the intensity of the spectrum at the ε_b values mentioned above. It was concluded that gold anodic oxidation, yielding most likely an Au(III) hydroxide surface layer, takes place in the E range of the anodic current wave beginning at E≈1.3 V. At E_B=1.7 V (the potential of the Burshtein minimum) the stationary surface layer consists of 2.5 to 3 molecular layers of Au(OH)₃. The theoretical amount of charge required for the reduction of one molecular layer of Au(OH)₃ is ∼0.15 mC cm⁻², since the Au(OH)₃ molecule is planar and occupies about four atomic sites on the electrode surface.     

Visualization of electron correlation in a series of helium S states

Electron correlation has been studied for a series of helium S states represented by a variety of wavefunctions, the best of which are accurate Hylleraas—Kinoshita functions. The states studied are the ground state, the lowest excited ¹S and ³S states, and the (2s)² and (2p)² doubly-excited ¹S states. Primary data is obtained from graphs of the conditional probability density as a function of the radial distance r₂ and the interelectronic angle θ₁₂, given that r₁ is fixed at various distances. Such graphs make clear the extent to which characteristics such as angular and radial correlations, and Fermi and Coulomb holes, are consequences of the relative motion of electrons in two-electron atoms.     

水滑石与海泡石复合材料对有机染料的光催化降解性能（英文）

由于ZnCr-LDH纳米粒子具有良好的光催化性能,但极易团聚,在一定程度上制约了它在光催化领域的应用.将水滑石制成核-壳复合材料可以避免粒子团聚,改善其单分散性和稳定性,从而提高光催化活性.本文设计了一种水滑石/海泡石(Sep@LDH)纳米复合材料作为光催化剂,以甲基橙(MO)和亚甲基蓝(MB)混合溶液模拟有机染料废水,进行光催化反应.通过XRD,SEM,UV-Vis DRS,PL,TG-DTG和BET/BJH,证明了水滑石成功的生长在海泡石的表面,通过光催化实验详细研究了Sep@LDH纳米复合材料的光催化性能及光降解反应机理.采用共沉淀制备了不同Zn/Cr摩尔比的水滑石纳米材料,对水滑石进行优化,结合表征分析,发现摩尔比为1的ZnCr-LDH其结晶度、层间规整度高,禁带宽度最窄(2.30 eV)和光致发光性能最佳.因而用作后续复合材料的制备.另一方面,我们以酸活化的海泡石(Sep)为载体,采用原位生长法成功制备了一种新型的水滑石/海泡石(Sep@LDH)光催化剂,研究了海泡石的添加量对复合材料性能的影响.结果表明,Sep含量对复合材料形貌、粒径大小、结构以及光学性质影响较大.其中,样品Sep_4@LDH(海泡石添加量为4 g),比表面积最大,因而光催化效率最高.降解动力学结果表明,染料的光降解过程遵循准一级动力学模型.我们通过对活性物种(·OH,h~+,·O_2~-)的考察,研究了光催化降解机理.结果表明,·OH在光降解过程中起着至关重要的作用.Sep_4@LDH复合材料循环使用5次后,MO和MB的光降解率依然分别可以达到86.2%和84.9%,表现出较高的稳定性.     

Sorption of aqueous palladium onto synthetic hydroxyapatite

The sorption of Pd(II) on hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂) has been studied at 25 °C as a function of pH, in 0.01 M NaClO₄, and 0.01 and 0.025 M Ca(ClO₄)₂ aqueous background electrolytes and Pd(II) concentration (9.3 to 47 ??M), trying to minimize some types of reactions, such as solid dissolution of and metal precipitation. The radiotracer palladium, ¹⁰⁹Pd, obtained by neutron irradiation, has been used to calculate the palladium??s distribution coefficients K _d between aqueous and solid phase. A mathematical treatment of results has been made by ion-exchange theory in order to interpret palladium sorption onto treated solid. For this, we take into account the existence of active sites at the hydroxyapatite surface, and the aqueous solution chemistry of palladium as well as the effect of phosphate anions from solid dissolution. The results can be explained as evidence of sorption of the species PdOH⁺, and of a mixed hydroxo complex of Pd²⁺ like (XCaO^?)?CPdOH⁺·nH₂O fixed onto {??Ca?COH} surface sites of the hydroxyapatite.     

An ab initio study of CO adsorption on ceria(1 1 0)

Hartree–Fock and DFT calculations are reported for the CO/CeO₂(1 1 0) surface system. The electron density, electrostatic potential, atomic charges and projected electronic density of states have been calculated from an ECP-and-point-charge-embedded cluster model and is compared with periodic calculations. The agreement between the two surface models is reasonably good. A number of weakly bonding CO adsorption sites were found, with E_ads (BSSE-corrected) ranging from 0.01 to 0.22 eV per adsorbed molecule. The two most favourable sites are found in the vicinity of surface cerium ions, with the CO molecule oriented in a tilted fashion, C-end down. The surface-induced CO stretching vibrational frequency shifts on these sites are a redshift of ≈−30 cm⁻¹ and a blueshift of ≈25 cm⁻¹, respectively.     

A flow microcalorimetric investigation of the acidity of chromium dioxide and γ-iron oxide

Investigations have been carried out to compare the acidity of surface sites on chromium dioxide and γ-iron oxide magnetic particles. Measured heats of adsorption and adsorption densities of pyridine show that surface sites on CrO₂, are more heterogeneous and more acidic than surface sites on γ-Fe₂O₃. Experimental results indicate that monolayer coverage of pyridine, approximately 5.0 μmol m⁻², is attained on CrO₂ at a solution concentration of approximately 35 mM. Application of the Freundlich isotherm to experimental results is discussed.     

Ni nanoparticles as electron-transfer mediators and NiSx as interfacial active sites for coordinative enhancement of H2-evolution performance of TiO2

The development of efficient photocatalytic H₂-evolution materials requires both rapid electron transfer and an effective interfacial catalysis reaction for H₂ production. In addition to the well-known noble metals, low-cost and earth-abundant non-noble metals can also act as electron-transfer mediators to modify photocatalysts. However, as almost all non-noble metals lack the interfacial catalytic active sites required for the H₂-evolution reaction, the enhancement of the photocatalytic performance is limited. Therefore, the development of new interfacial active sites on metal-modified photocatalysts is of considerable importance. In this study, to enhance the photocatalytic evolution of H₂ by Ni-modified TiO₂, the formation of NiS_x as interfacial active sites was promoted on the surface of Ni nanoparticles. Specifically, the co-modified TiO₂/Ni-NiS_x photocatalysts were prepared via a two-step process involving the photoinduced deposition of Ni on the TiO₂ surface and the subsequent formation of NiS_x on the Ni surface by a hydrothermal reaction method. It was found that the TiO₂/Ni-NiS_x photocatalysts exhibited enhanced photocatalytic H₂-evolution activity. In particular, TiO₂/Ni-NiS_x(30%) showed the highest photocatalytic rate (223.74 μmol h^?1), which was greater than those of TiO₂, TiO₂/Ni, and TiO₂/NiS_x by factors of 22.2, 8.0, and 2.2, respectively. The improved H₂-evolution performance of TiO₂/Ni-NiS_x could be attributed to the excellent synergistic effect of Ni and NiS_x, where Ni nanoparticles function as effective mediators to transfer electrons from the TiO₂ surface and NiS_x serves as interfacial active sites to capture H⁺ ions from solution and promote the interfacial H₂-evolution reaction. The synergistic effect of the non-noble metal cocatalyst and the interfacial active sites may provide new insights for the design of highly efficient photocatalytic materials.     

Absolute detection of metastable rare gas atoms by a cw laser photoionization method

A novel, accurate method for the absolute detection of metastable rare gas atoms is described and demonstrated. It involves a direct in situ determination of the electron emission coefficient γ for impact of the respective metastable atom on a conducting surface. γ is reliably obtained by a cw two-photon ionization — depletion technique: the reduction ΔI _S in electron current from the detector surface due to efficient photoionization removal of the metastable flux is compared with the photoelectron current ΔI _P (γ = ΔI _S/ΔI _P). The principle of the method, possible realization schemes for the different metastable rare gas atoms and the apparatus are described in detail. The method has been applied so far to metastable Ne* (3s ³ P ₂), Ar* (4s ³ P ₂), and Kr* (5s ³ P ₂) atoms, and corresponding results for γ, obtained with five different chemically clean, polycrystalline surface materials and at two surface temperatures (300 K, 360 K) are reported. Whereas for Ne*, the value of γ (≈0.35) showed only a rather weak dependence on the surface material and temperature (as also found for a mixed He* (2³ S, 2¹ S) beam), strong variations in γ, especially at 300 K, were detected for Ar* and Kr* (values between 0.25 and 0.003). Some applications of the described method, especially with regard to the determination of absolute reaction cross sections involving metastable rare gas atoms, are discussed.     

Liquid-phase hydrogenation of 1-alkenes over Rh/AlPO4 and Rh/sepiolite catalysts

The catalytic activity of Rh (1 wt.%) catalysts supported on AlPO₄ and sepiolite has been studied in the liquid-phase hydrogenation of linear 1-alkenes. The reaction orders with respect to 1-alkene concentration are negative but are first order with respect to hydrogen, indicating that 1-alkene adsorbs very strongly on Rh sites and alkene and H₂, compete for adsorption sites on the surface. The initial hydrogenation rates increase in the order 1-hexene < 1-heptene < 1-octene, and furthermore, on going from 1-hexene to 1-octene the steric effects (through ΔS^≠) are activating, while electronic effects (from ΔH^≠) deactivate the reaction process. A cis-concerted mechanism taking place in a single step on a Rh site with three coordinative unsaturations which can simultaneously adsorb hydrogen and a π-bonded alkene is suggested.     

Layer-by-layer enriching active Ni-N3C sites in nickel-nitrogen-carbon electrocatalysts for enhanced CO2-to-CO reduction

Transition metal and nitrogen co-doped carbons (M-N-C) have proven to be promising catalysts for CO₂ electroreduction into CO because of the high activity and selectivity. Effective enrichment of the active transition metal coordinated nitrogen sites is desirable but is challenging for a practical volumetric productivity. Herein, we report four kinds of model electrocatalysts to unveil this issue, which include the NC structures with surface N-functionalities, Ni-N-C_I with one layer of surface Ni-N₃C sites, NC@Ni-N-C_I with surface N-functionalities and underneath Ni-N₃C sites as well as Ni-N-C_II with doubled surface Ni-N₃C sites. The X-ray absorption spectroscopy indicates the coordination configuration of Ni-N₃C. For NC catalysts, when N-doping level increased from 3.5 at% to 8.4 at%, the CO partial current density increased from below 0.1 mA/cm² to 3 mA/cm². Introducing one layer of Ni-N₃C onto the NC structures leads to a 54 times higher CO partial current density than that of NC, in the meantime the FE_CO is 66 times higher. Furthermore, doubling the density of surface Ni-N₃C sites by a layer-by-layer method doubles the CO partial current density (j_CO), indicating its potential to achieve a high density of active coordinated sites and current densities.