The catalytic performance of metal-free defected carbon catalyst towards acetylene hydrochlorination revealed from first-principles calculation

Defected carbon materials as a metal-free catalyst have shown superior stability and catalytic performance in the acetylene hydrochlorination reaction. Through density functional theory (DFT) calculations, for the first time, several different defected configurations comprising mono and divacancies and Stone Wales defect on single-walled carbon nanotubes (SWCNTs) have been used as a direct catalyst for acetylene hydrochlorination reaction. These defective sites on SWCNTs are the most active site for acetylene hydrochlorination reaction compare to pristine SWCNT. The different configurations of defects have different electronic structures, which specify that monovacancy defects have more states adjacent to the Fermi level. The reactant acetylene (C₂H₂) adsorbed strongly compared to hydrogen chloride (HCl) and expected to be the initial step of the reaction. Acetylene adsorbed strongly at monovacancy defected SWCNT compared to other investigated defects. Reaction pathway analysis revealed that mono- and divacancy defected SWCNTs have minimum energy barriers and show extraordinary performance toward acetylene hydrochlorination. This work suggests the potential of metal-free defected carbon in catalyzing acetylene hydrochlorination and provides a solid base for future developments in acetylene hydrochlorination.     

Effect of the nature of carbonaceous supports on the bioelectrocatalytic activity of peroxidase, immobilized on the supports, in the hydrogen peroxide reduction reaction

Electrochemical properties of such disperse carbonaceous materials as acetylene black AD-100, finely divided colloidal graphite (FCG), ultradisperse diamond (UDD), and carbon nanotubes (CNT) are examined. Effect of the nature of disperse carbonaceous supports on bioelectrocatalytic activity of adsorbed peroxidase (POD) in the hydrogen peroxide reduction reaction is investigated. It is shown that the hydrogen peroxide reduction on the biocatalysts studied proceeds in conditions of direct bioelectrocatalysis independently of the disperse-support type. It is also demonstrated that the biocatalysts’ activity depends on the structure and properties of the surface of the supports defining the magnitude of the POD adsorption in an orientation favorable for direct bioelectrocatalysis. Maximum activity is inherent in the catalysts manufactured on the basis of materials with moderate hydrophobic and hydrophilic properties. By the magnitude of the activity in the hydrogen peroxide reduction reaction, depending on the nature of the carbonaceous support, the fabricated catalysts (carbonaceous material with adsorbed POD) form the series AD-100, CNT > FCG > UDD.     

Mechanism of initiation in the γ-radiation-induced polymerization of ethylene

The relation between the gaseous products and the reaction conditions such as pressure, temperature, and dose rate in the γ-radiation-induced polymerization of ethylene was studied. The main gaseous products were hydrogen and acetylene, and the amounts of these products increased linearly with reaction time, monomer density, and dose rate, while they were independent of reaction temperature. The ratio of rate of formation of hydrogen to acetylene was about one-half. Further, it was found that the number of moles of polymer chain formed was almost equal to that of acetylene at room temperature. An initiation mechanism in which both hydrogen and acetylene are formed is proposed. The equation which is derived on the basis of the initiation mechanism is shown to be in good accordance with the experimental results.     

Pd8簇催化氢化乙炔的反应机理

采用密度泛函理论(DFT)中的B3PW91方法研究了过渡金属Pd₈簇催化氢化乙炔的反应机理. 研究表明: H₂进入Pd₈簇后解离成H原子, 并且只有当H原子吸附在Pd₈簇表面上时, 催化氢化反应才能发生. 过渡金属Pd₈簇催化氢化乙炔的反应机理的研究证实该催化反应从两种反应物出发经过两条不同的反应途径完成催化氢化反应, 两种反应物分别为吸附在Pd₈簇上的乙炔(Pd₈(2H)－CH＝CH)和其同分异构体亚乙烯基吸附物(Pd₈(2H)－C＝CH₂). 两条途径均为多步连续的加氢反应, 不同之处在于从Pd₈(2H)－CH＝CH出发的为单一路径, 解离后的H原子分步依次加成到吸附在Pd₈簇上的乙炔中的C原子上, 直到反应完成生成乙烷. 而从Pd₈(2H)－C＝CH₂出发的路径较为复杂, 分别经过两个不同的过渡态和中间体生成次乙基中间体, 该过程相对应的反应位垒相差约12.552 kJ·mol^-1, 说明这两个过渡态同时存在, 无先后次序. 然后继续加成H原子直到生成乙烷完成反应. 同时, 两条路径分别形成一系列具有应用价值的C₂有机化合物中间体, 其中一些中间体通过分子内质子转移相互转化, 使得原本独立的两条反应路径联系在一起, 成为网状路径.     

C2H2在Ru(1010)表面上的分子轨道对称性

利用角分辨紫外光电子能谱对低温下（160 K）乙炔（C2H2）气体在Ru()表面的吸附 进行了研究.实验结果表明：乙炔的C-C轴并不平行于衬底表面, C-C轴在<0001>晶向和表 面法线组成的平面内有一定的倾斜.与气相乙炔分子不同,在Ru()表面吸附的乙炔分子的C-H 轴不是沿C-C轴向.     

Effect of acetylene on the γ-radiation-induced polymerization of ethylene

The effects of acetylene on the γ-radiation-induced polymerization of ethylene were studied from the viewpoint of the gaseous products and polymer structure. The experiments were carried out under a pressure of 400 kg/cm²; the temperature was 30°C; the does rate was 1.1 × 10⁵ rad/hr; and the acetylene content was 0–20%. The solid polymer was obtained in the polymerization of ethylene containing 2.2% acetylene, while the monomer containing 19.7% acetylene gave a yellowish viscous oil. The polymer yield and molecular weight decreased remarkably with acetylene content. The main gaseous product was hydrogen, and trace amounts of butane, butene-1, butadiene-1,3, and benzene and its derivatives were also observed. The rate of formation of hydrogen was almost independent of acetylene content and there was no difference in acetylene contents before and after the irradiation was found. The infrared spectra of the polymers showed the presence of vinylidene, trans-vinylene, and terminal vinyl unsaturations, 1,4-disubstituted benzene, and carbonyl groups. The contents of trans-vinylene, terminal vinyl, and methyl groups increased with acetylene content, and that of vinylidene was independent of acetylene content. The monomer reactivity ratios of ethylene and acetylene were evaluated as 45.5 and 66.0, respectively. On the basis of the results, the effects of acetylene on the γ-radiation-induced polymerization of ethylene were discussed.     

Structural, electronic, and vibrational properties of acetylene on Pd(100) doped with Sn or Pb: A DFT cluster model study

Some structural, electronic, and vibrational properties of the acetylene (C₂H₂) molecule adsorbed at various sites on the Pd(100) surface doped with Sn or Pb are determined theoretically. The calculations were performed using the B3LYP hybrid density functional, and the Sn- or Pb-doped Pd(100) surfaces were represented by a cluster model approach. It is found that the geometry of the C₂H₂ molecule adsorbed in di- σ configurations is highly perturbed with respect to the structure of acetylene in the gas phase. By contrast, the geometry of acetylene adsorbed in π configurations on the doped surfaces shows a much smaller distortion. Apart from calculating the properties of the adsorbed C₂H₂ molecule, the effect of the dopants, i.e. Sn and Pb atoms, on these properties is established by comparing the properties of acetylene adsorbed on the Sn- or Pb-doped Pd(100) surfaces with its properties on the monometallic Pd(100) surface. The results indicate that the geometry of the adsorbed C₂H₂ molecule is similar on the doped and monometallic Pd(100) surfaces.     

The thermodynamic characteristics of processes in Raney nickel surface layers with the participation of adsorbed hydrogen forms

Equilibria between adsorbed hydrogen forms on the surface of Raney nickel in aqueous solutions were studied by the potentiometric and adsorption-calorimetric methods. The establishment of equilibria between adsorbate forms was proved experimentally. The model of a surface with discrete inhomogeneity was used to determine the standard thermodynamic characteristics of surface equilibria and adsorption of particular hydrogen adsorption forms. The influence of pH of the bulk phase on the thermodynamic characteristics of adsorption of hydrogen on the surface of Raney nickel caused redistribution of adsorbed hydrogen forms.     

可逆与不可逆吸附氢在合成甲醇反应中的作用

在自行设计和建立的加压动态分析装置上研究了合成甲醇催化剂上氢的吸附和反应行为。结果表明:在反应条件下催化剂上吸附的氢可分为可逆吸附氢和不可逆吸附氢;不可逆吸附氢又可分为能被CO顶替出来的和不能被CO顶替出来的两部分;能被CO顶替出来的不可逆吸附氢对CO的吸附起促进作用,不能被CO顶替出来的不可逆吸附氢是合成甲醇催化剂必不可少的“组分”或称“促进剂”;同时甲醇的生成是可逆吸附氢与一氧化碳作用的结果。     

Reactivity of the Indenyl Radical (C9H7) with Acetylene (C2H2) and Vinylacetylene (C4H4)

The reactions of the indenyl radicals with acetylene (C₂H₂) and vinylacetylene (C₄H₄) is studied in a hot chemical reactor coupled to synchrotron based vacuum ultraviolet ionization mass spectrometry. These experimental results are combined with theory to reveal that the resonantly stabilized and thermodynamically most stable 1-indenyl radical (C₉H₇^.) is always formed in the pyrolysis of 1-, 2-, 6-, and 7-bromoindenes at 1500 K. The 1-indenyl radical reacts with acetylene yielding 1-ethynylindene plus atomic hydrogen, rather than adding a second acetylene molecule and leading to ring closure and formation of fluorene as observed in other reaction mechanisms such as the hydrogen abstraction acetylene addition or hydrogen abstraction vinylacetylene addition pathways. While this reaction mechanism is analogous to the bimolecular reaction between the phenyl radical (C₆H₅^.) and acetylene forming phenylacetylene (C₆H₅CCH), the 1-indenyl+acetylene→1-ethynylindene+hydrogen reaction is highly endoergic (114 kJ mol⁻¹) and slow, contrary to the exoergic (−38 kJ mol⁻¹) and faster phenyl+acetylene→phenylacetylene+hydrogen reaction. In a similar manner, no ring closure leading to fluorene formation was observed in the reaction of 1-indenyl radical with vinylacetylene. These experimental results are explained through rate constant calculations based on theoretically derived potential energy surfaces.     

Electronic excited states of Si(100) and organic molecules adsorbed on Si(100)

The electronically excited states of the Si(100) surface and acetylene, benzene, and 9,10-phenanthrenequinone adsorbed on Si(100) are studied with time-dependent density functional theory. The computational cost of these calculations can be reduced through truncation of the single excitation space. This allows larger cluster models of the surface in conjunction with large adsorbates to be studied. On clean Si(100), the low-lying excitations correspond to transitions between the pi orbitals of the silicon-silicon dimers. These excitations are predicted to occur in the range 0.4-2 eV. When organic molecules are adsorbed on the surface, surface --> molecule, molecule --> surface, and electronic excitations localized within the adsorbate are also observed at higher energies. For acetylene and benzene, the remaining pipi* excitations are found to lie at lower energies than in the corresponding gas-phase species. Even though the aromaticity of 9,10-phenanthrenequinone is retained, significant shifts in the pipi* excitations of the aromatic rings are predicted. This is in part due to structural changes that occur upon adsorption.     

Effects of surfactants on the electroreduction of dioxygen at an acetylene black electrode.

An acetylene black electrode modified by an adsorbed cationic surfactant, cetyltrimethylammonium bromide (CTAB), was developed. The influences of various types of surfactants on the electroreduction of O2 were investigated. It was demonstrated that a cationic surfactant, CTAB, on the surface of the electrode could significantly decrease the overpotential of dioxygen reduction, and the reduction peak current of O2 was also remarkably increased. The reduction of O2 at a CTAB modified acetylene black electrode was studied using cyclic voltammetry, chronocoulometry and controlled potential coulometry. The total number of electrons, the exchange current density (j(o)) and the transfer coefficient (alpha) for reduction of O2 at the surface of this modified electrode were determined.     

Molecular orbital study of the selective hydrogenation of acetylene in aqueous metalcatalyzed tetrahydroborate systems

A computer program for geometry optimization based on a multivariate regression method is discussed. The configuration of the adsorbed species of acetylene on copper, silver and gold catalysts were obtained at the usual CNDO level. The adsorbed species of acetylene on copper and gold catalysts are M(ν² - C₂H₂) complexes, whereas that on silver is of vinyl form. The electronic-charge distribution, energy partitions and total Mulliken overlap population suggested that acetylene is effectively activated in these systems.     

Acetylene Pyrolysis in Tubular Reactor

Pyrolysis of acetylene was investigated in a tubular reactor of graphite with an internal lining of alumina. The temperature range was 850–1650 °C, and the pressure was about 0.133 bar (100 Torr). Pure acetylene and acetylene diluted with argon or hydrogen were used as feed. Carbon and hydrogen are the main products from acetylene pyrolysis particularly at higher conversion. At lower conversion of acetylene, other gas products were formed; the amount of these depended on temperature, dilution, and conversion. Benzene and vinyl acetylene are the main gas products from pyrolysis of pure acetylene below 1000 °C and at low conversion. Diacetylene increases with increasing temperature. Dilution with hydrogen changes the composition of the gas product, decreases the selectivity of vinyl acetylene and benzene, and increases the formation of methane and ethylene. Gas‐phase equilibrium may be approached between some components. The conversion of acetylene with argon dilution and low conversion was found to be of second order. Pyrolysis of pure acetylene at lower temperature and low conversion gave the rate constant k = 3.1 × 10⁹ · exp(?34.8/RT) L mol^?1 s^?1 with an activation energy of 34.8 kcal mol^?1. The initial reaction at 864 °C is a molecular formation of vinyl acetylene. The initial activation of acetylene in gas phase seems to be rate determining and of second order in acetylene. Decomposition of acetylene can take place both homogeneously and heterogeneously. Above a critical partial pressure of acetylene, the decomposition is apparently explosive with instant plugging of the reactor with carbon.     

负载型Pd/TiO2和Pd-Ag/TiO2催化剂的乙炔选择性加氢催化性能

利用程序升温还原(TPR)、X-射线衍射(XRD)、CO吸附-红外光谱(CO-IR)、电子顺磁共振(EPR)和微型催化反应评价等手段, 研究了负载Pd/γ-Al2O3, Pd/TiO2和Pd-Ag/TiO2催化剂的结构和乙炔选择性加氢催化性能. 结果表明, Pd/TiO2催化剂具有较Pd/γ-Al2O3催化剂更优良的乙炔选择性加氢催化性能, 这与Pd-TiO2之间的强相互作用密切相关. Pd-TiO2之间的强相互作用不仅使负载型钯金属催化剂具有较高的乙炔加氢催化选择性, 而且具有较高的乙炔加氢催化活性. Pd/TiO2催化剂中添加Ag 组分后, Pd金属可促进Ag+的还原并可能形成Pd-Ag合金, 催化剂的乙烯选择性虽有所增加, 但乙炔转化率和乙烯收率下降.     

CATALYTIC ACTIVITY OF Pd-Sn COMPLEX CARBONYLATION OF ACETYLENE

The influence of different concentration of HO, SnCl2, Cl- and n-BuOH on the carbonylation of acetylene has been studied. The results show that the yield of n- butyl propionate increases with the increase of HC1 concentration and the catalytic activity is depressed when Cl" concentration increases. However, the stability of catalytic complex is promoted by Cl-. The key to the carbonylation of acetylene lies in the addition of SnCl2, which promotes the formation of the complex of C2H2, CO with catalyst and plays an important role in the hydrogen removal from n-BuOH. The hydrogen removed from n BuOH is the hydrogen source of this reaction. Meanwhile, the principle of the effect of HCl, Cl- and SnCl2 on reaction has been discussed. The reaction model has also been proposed.     

Reaktionskinetische Untersuchungen der Hydratisierung von Acetylen zu Acetaldehyd an Molekularsieben,die mit katalytisch wirksamen Metall-Ionen beladen sind

The kinetics of the catalytic hydration of acetylene to acetaldehyde in the gas-phase by incorporation of catalytic metal ions on molecular sieves has been studied in a differential reactor. The main product was acetaldehyde besides of small amounts of crotonaldehyde and acetic acid. The catalysts [cadmium(II)-, zinc(II)-, copper(II)- and silver(I)-13 X-molecular sieves] were deactivated at a rate proportional to the square of the hydration rate. The initial hydration rate calculated on the basis of this relation was first order in the acetylene concentration. Starting rate of hydration and rate of deactivation increase with increasing concentration of metal ions on the sieve. The temperature dependence of the rate follows the law of Arrhenius The activation energies of hydration and deactivation, respectively, were calculated. Pore diffusion is a limiting factor. The poison is homogeneously deposited on the catalyst and weakly adsorbed, as it is shown by the criterion of Wheeler. The rate of deactivation decreases with increasing water/acetylene ratio. The deactivation rate which is due to deposition of polymerised acetylene and/or acetaldehyde, is slow with zinc and cadmium catalysts, and more rapid with copper and silver catalysts.     

Effects of the nature and composition of the solvent on the thermodynamic characteristics of the individual forms of hydrogen adsorbed on the surface of porous nickel

The effects of the nature and composition of solvents on the thermodynamic characteristics of the adsorption states of hydrogen on nickel were studied. The adsorption can be described in terms of the thermodynamic model of a surface with a discrete nonhomogeneity for three individual forms of adsorbed hydrogen. The thermodynamic characteristics of the individual forms of hydrogen adsorbed on porous nickel from aqueous solutions of sodium hydroxide, dimethylformamide, methanol, and ethanol were determined.     

Infrared studies of the effect of acetylene, hydrogen, and oxygen on CO adsorption on platinum hydrosols

Infrared spectra of CO-treated platinum hydrosols subsequently treated with acetylene, hydrogen, and oxygen reveal that v(CO)_ads decreases from 2070 cm⁻¹ with increasing gas-treatment time. This has been attributed to a reduction in the coverage of adsorbed CO. In Pt sol/CO/C₂H₂ systems, v(CO)_ads decreases to a limiting value of ca. 2060 cm⁻¹ after exposure to acetylene. In the Pt sol/CO/H₂ systems, v(CO)_ads decreases to ca. 2050 cm⁻¹ after exposure to hydrogen gas. The lower frequency in the Pt sol/CO/H₂ system has been attributed to CO adsorption on more active metal sites formed from the reduction of surface platinum oxides. Exposure of the CO-treated platinum hydrosols to O₂ gas was found to cause the eventual disappearance of the v(CO)_ads band in infrared spectra, which was attributed to oxidation of adsorbed CO to CO₂ by weakly bound surface layers of platinum oxides formed by the oxygen treatment.     

Mathematical Modeling of the Plasma-Chemical Pyrolysis of Methane

A mathematical model was developed for the plasma-chemical pyrolysis of methane, which includes the latest data on the mechanism and kinetics of chemical processes of hydrocarbon pyrolysis and mixing of methane jets with hydrogen heated in an arc plasma torch. The results of calculations on methane conversion and the synthesis of acetylene and its homologues satisfactorily agree with experimental data over a wide range of parameters of the process. It was shown that the methane conversion is initiated via interaction with atomic hydrogen, acetylene is produced through the dissociation of intermediate products involving radicals, and the consumption of acetylene is due to the synthesis of its homologues involving vinylidenecarbene and methylenecarbene in the ground and excited states.