Site- and surface species-dependent propylene oxidation with molecular oxygen on gold surface

A complete fundamental understanding of propylene oxidation with molecular O₂ on Au surface is achieved, in which site-and surface species-dependent reaction behaviors are revealed.     

Selective CO2 Electroreduction to Ethylene and Multicarbon Alcohols via Electrolyte‐Driven Nanostructuring

Production of multicarbon products (C₂₊) from CO₂ electroreduction reaction (CO₂RR) is highly desirable for storing renewable energy and reducing carbon emission. The electrochemical synthesis of CO₂RR catalysts that are highly selective for C₂₊ products via electrolyte‐driven nanostructuring is presented. Nanostructured Cu catalysts synthesized in the presence of specific anions selectively convert CO₂ into ethylene and multicarbon alcohols in aqueous 0.1 m KHCO₃ solution, with the iodine‐modified catalyst displaying the highest Faradaic efficiency of 80 % and a partial geometric current density of ca. 31.2 mA cm^?2 for C₂₊ products at ?0.9 V vs. RHE. Operando X‐ray absorption spectroscopy and quasi in situ X‐ray photoelectron spectroscopy measurements revealed that the high C₂₊ selectivity of these nanostructured Cu catalysts can be attributed to the highly roughened surface morphology induced by the synthesis, presence of subsurface oxygen and Cu⁺ species, and the adsorbed halides.     

Experimental Investigation on Upgrading of Lignin‐Derived Bio‐Oils: Kinetic Analysis of Anisole Conversion on Sulfided CoMo/Al2O3 Catalyst

Kinetics of the hydroprocessing of anisole, a compound representative of lignin‐derived bio‐oils, catalyzed by a commercial sulfided CoMo/Al₂O₃, was determined at 8–20 bar pressure and 573–673 K with a once‐through flow reactor. The catalyst was sulfided in an atmosphere of H₂ + H₂S prior to the measurement of its performance. Selectivity‐conversion data were used as a basis for determining an approximate, partially quantified reaction network showing that hydrodeoxygenation (HDO), hydrogenolysis, and alkylation reactions take place simultaneously. The data indicate that these reactions can be stopped at the point where HDO is virtually completed and hydrogenation reactions (and thus H₂ consumption) are minimized. Phenol was the major product of the reactions, with direct deoxygenation of anisole to give benzene being kinetically almost insignificant under our conditions. We infer that the scission of the C_methyl–O bond is more facile than the scission of the C_aromatic–O bond, so that the HDO of anisole likely proceeds substantially through the reactive intermediate phenol to give transalkylation products such as 2‐methylphenol. The data determine rates of formation of the major primary products. The data show that if oxygen removal is the main processing goal, higher temperatures and lower pressures are favored.     

Regeneration of C4H10 dry reforming catalyst by nonthermal plasma

Carbon deposition via coke formation is one of the critical problems causing catalyst deactivation during the reforming of hydrocarbons. An effort was made to regenerate the catalyst (Ni/γ-alumina) by oxidation methods. Two approaches were carried out for the regeneration of the deactivated catalyst. The first one involves the plasma treatment of the deactivated catalyst in the presence of dry air over a temperature range of 300～500 °C, while the second one only the thermal treatment in the same temperature range. The performance of the regenerated catalyst was evaluated in terms of C₄H₁₀ and CO₂ conversions and the physicochemical characteristics were examined using a surface area analyzer, an elemental analyzer, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was observed that the carbon deposit (coke) on the catalyst was about 9.89 wt% after reforming C₄H₁₀ for 5 h at 540 °C. The simple thermal treatment at 400 °C reduced carbon content to 6.59 wt% whereas it was decreased to 3.25 wt% by the plasma and heat combination. The specific surface area was fully restored to the original state by the plasma-assisted regeneration at 500 °C. As far as the catalytic activity is concerned, the fresh and regenerated catalysts exhibited similar C₄H₁₀ and CO₂ conversion efficiencies.     

Coupling Benzylamine Oxidation with CO2 Photoconversion to Ethanol over a Black Phosphorus and Bismuth Tungstate S-Scheme Heterojunction

Photoconversion of CO₂ and H₂O into ethanol is an ideal strategy to achieve carbon neutrality. However, the production of ethanol with high activity and selectivity is challenging owing to the less efficient reduction half-reaction involving multi-step proton-coupled electron transfer (PCET), a slow C−C coupling process, and sluggish water oxidation half-reaction. Herein, a two-dimensional/two-dimensional (2D/2D) S-scheme heterojunction consisting of black phosphorus and Bi₂WO₆ (BP/BWO) was constructed for photocatalytic CO₂ reduction coupling with benzylamine (BA) oxidation. The as-prepared BP/BWO catalyst exhibits a superior photocatalytic performance toward CO₂ reduction, with a yield of 61.3 μmol g⁻¹ h⁻¹ for ethanol (selectivity of 91 %).In situ spectroscopic studies and theoretical calculations reveal that S-scheme heterojunction can effectively promote photogenerated carrier separation via the Bi−O−P bridge to accelerate the PCET process. Meanwhile, electron-rich BP acts as the active site and plays a vital role in the process of C−C coupling. In addition, the substitution of BA oxidation for H₂O oxidation can further enhance the photocatalytic performance of CO₂ reduction to C₂H₅OH. This work opens a new horizon for exploring novel heterogeneous photocatalysts in CO₂ photoconversion to C₂H₅OH based on cooperative photoredox systems.     

Mechanistic Insight into the Catalytic Oxidation of Cyclohexane over Carbon Nanotubes: Kinetic and In Situ Spectroscopic Evidence

As some of the most interesting metal‐free catalysts, carbon nanotubes (CNTs) and other carbon‐based nanomaterials show great promise for some important chemical reactions, such as the selective oxidation of cyclohexane (C₆H₁₂). Due to the lack of fundamental understanding of carbon catalysis in liquid‐phase reactions, we have sought to unravel the role of CNTs in the catalytic oxidation of C₆H₁₂ through a combination of kinetic analysis, in situ spectroscopy, and density functional theory. The catalytic effect of CNTs originates from a weak interaction between radicals and their graphene skeletons, which confines the radicals around their surfaces. This, in turn, enhances the electron‐transfer catalysis of peroxides to yield the corresponding alcohol and ketone.     

Evolution of H2O and CO2 during the copper-catalyzed oxidation of isotactic polypropylene

The kinetics and mechanism of H₂O and CO₂ evolution during uncatalyzed and copper(oxide)-catalyzed (Cu, CuO, CuO_0.67) oxidation of isotactic polypropylene have been investigated in detail for various catalysts over a range of temperatures (90–150°C). These volatiles were determined chromatographically; H₂O and CO₂ represent the main volatiles of the oxidation, comprising about 80 mol % of all volatiles. Uncatalyzed oxidation evolves ca. 1 mol of H₂O and 1 mol of CO₂ for each unit mole of polymer oxidized, while catalyzed oxidation produces 2 mol of H₂O and ca. 1.2 mol of CO₂ for each unit mole of polymer. These results indicate that secondary as well as tertiary H atoms on the polymer chains are involved in hydroperoxide formation and decay. The oxidation mechanism has been formulated and evaluated on this basis. It consists essentially of two parallel oxidation reactions involving tertiary and secondary groups (H atoms and hydroperoxides), respectively. The mechanism can be represented by first- and pseudo-first-order reactions in series: (1) oxygen absorption showing induction periods; (2) hydroperoxide formation and decay (plateaus are reached); (3) H₂O evolution from the decay of hydroperoxides; and (4) subsequent CO₂ production involving chain scission. Arrhenius parameters for all oxidation reactions (uncatalyzed and catalyzed) are also presented. It appears that CuO_0.67 is the most efficient catalyst of those investigated.     

Oxidative interactions of propene with acetic acid on a Pd-zeolite catalyst

The interactions between C₃H₆, AcOH and O₂ were investigated on 1.5 % Pd/TsVM catalysts prepared with and without addition of 15 % AcOK. Three states for surface oxygen on the promoted catalyst were distinguished. Two of them are involved in the oxidation of AcOH and C₃H₆ to CO₂ and H₂O, whereas the adsorbed species of the third type participates in the formation of allyl acetate. The O/Pd ratios for the promoted catalyst fall in the range from 3 to 4, the nonpromoted system is characterized by an O/Pd value of 0.5. IR-spectral data are used to discuss the reaction scheme for the formation of allyl acetate. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1721–1726, October, 1993.     

富氧条件下乙炔选择催化还原NOx

Acetylene as a reducing agent of metal exchanged HY catalysts, for selective catalytic reduction of NO in the reaction system of 0.16% NO, 0 （C2H2-SCR） was investigated over a series 08% C2H2, and 9.95% O2 （volume percent） in He. 75% of NO conversion to N2 with hydrocarbon efficiency about 1.5 was achieved over a Ce-HY catalyst around 300 ℃. The NO removal level was comparable with that of selective catalytic reduction of NOx by C3H6 reported in literatures, although only one third of the reducing agent in carbon moles was used in the C2H2-SCR of NO. The protons in zeolite were crucial to the C2H2-SCR of NO, and the performance of HY in the reaction was significantly promoted by cerium incorporation into the zeolite. NO2 was proposed to be the intermediate of NO reduction to N2, and the oxidation of NO to NO2 was rate-determining step of the C2H2-SCR of NO over Ce-HY. The suggestion was well supported by the results of the NO oxidation with O2, and the C2H2 consumption under the conditions in the presence or absence of NO.     

Electrocatalytic CO2 Upgrading to Triethanolamine by Bromine-Assisted C2H4 Oxidation

The electrocatalytic carbon dioxide (CO₂) reduction is a promising approach for converting this greenhouse gas into value-added chemicals, while the capability of producing products with longer carbon chains (C_n>3) is limited. Herein, we demonstrate the Br-assisted electrocatalytic oxidation of ethylene (C₂H₄), a major CO₂ electroreduction product, into 2-bromoethanol by electro-generated bromine on metal phthalocyanine catalysts. Due to the preferential formation of Br₂ over *O or Cl₂ to activate the C=C bond, a high partial current density of producing 2-bromoethanol (46.6 mA⋅cm⁻²) was obtained with 87.2 % Faradaic efficiency. Further coupling with the electrocatalytic nitrite reduction to ammonia at the cathode allowed the production of triethanolamine with six carbon atoms. Moreover, by coupling a CO₂ electrolysis cell for in situ C₂H₄ generation and a C₂H₄ oxidation/nitrite reduction cell, the capability of upgrading of CO₂ and nitrite into triethanolamine was demonstrated.     

Catalytic Oxidation of Methane to C2‐C4 Hydrocarbons over CeO2 Promoted W‐Mn/SiO2 Catalysts at Higher Pressure

CeO₂‐promoted Na‐Mn‐W/SiO₂ catalyst has been studied for catalytic oxidation of methane in a micro‐stainless‐steel reactor at elevated pressure. The effect of operating conditions, such as GHSV, pressure and CH₄/O₂ ratio, has been investigated. 22.0% CH₄ conversion with 73.8% C₂‐C₄ selectivity (C₂/C₃/C₄ = 3.8/1.0/3.6) was obtained at 1003 K, 1.5 × 10⁵ h^?;1 GHSV and 1.0 MPa. The results show: Elevated pressure disadvantages the catalytic oxidation of methane to C₂‐C₄ hydrocarbons. Large amounts of C₃ and C₄ hydrocarbons are observed. The unfavorable effects of elevated pressure can be overcome by increasing GHSV; the reaction is strongly dependent on the operating conditions at elevated pressure, particularly dependent on GHSV and ratio of CH₄/O₂. Analyses by means of XRD, XPS and CO₂‐TPD show that CO₂ produced from the reaction makes a weakly poisoning capacity of the catalyst; information of changeful valence on Ce and Mn was detected over the near‐surface of the Ce‐Na‐W‐Mn/SiO₂ catalyst; the existence of Ce³⁺/Ce⁴⁺ and Mn²⁺/Mn³⁺ ion couple supported that the reaction over the catalyst followed the Redeal‐Redox mechanism. Oxidative re‐coupling of C₂H₆ and CH₄ in gas phase or over surface of catalyst produces C₃ or C₄ hydrocarbons.     

Highly Efficient Conversion of Propargylic Amines and CO2 Catalyzed by Noble‐Metal‐Free [Zn116] Nanocages

The reaction of propargylic amines and CO₂ can provide high‐value‐added chemical products. However, most of catalysts in such reactions employ noble metals to obtain high yield, and it is important to seek eco‐friendly noble‐metal‐free MOFs catalysts. Here, a giant and lantern‐like [Zn₁₁₆] nanocage in zinc‐tetrazole 3D framework [Zn₂₂(Trz)₈(OH)₁₂(H₂O)₉?8 H₂O]_n Trz=(C₄N₁₂O)^4? ( 1 ) was obtained and structurally characterized. It consists of six [Zn₁₄O₂₁] clusters and eight [Zn₄O₄] clusters. To our knowledge, this is the highest‐nuclearity nanocages constructed by Zn‐clusters as building blocks to date. Importantly, catalytic investigations reveal that 1 can efficiently catalyze the cycloaddition of propargylic amines with CO₂, exclusively affording various 2‐oxazolidinones under mild conditions. It is the first eco‐friendly noble‐metal‐free MOFs catalyst for the cyclization of propargylic amines with CO₂. DFT calculations uncover that Zn^II ions can efficiently activate both C≡C bonds of propargylic amines and CO₂ by coordination interaction. NMR and FTIR spectroscopy further prove that Zn‐clusters play an important role in activating C≡C bonds of propargylic amines. Furthermore, the electronic properties of related reactants, intermediates and products can help to understand the basic reaction mechanism and crucial role of catalyst 1 .     

Mechanism of the Cycloaddition of Carbon Dioxide and Epoxides Catalyzed by Cobalt‐Substituted 12‐Tungstenphosphate

Co^II‐substituted α‐Keggin‐type 12‐tungstenphosphate [(n‐ C₄H₉)₄N]₄H[PW₁₁Co(H₂O)O₃₉]‐ (PW₁₁Co) is synthesized and used as a single‐component, solvent‐free catalyst in the cycloaddition reaction of CO₂ and epoxides to form cyclic carbonates. The mechanism of the cycloaddition reaction is investigated using DFT calculations, which provides the first computational study of the catalytic cycle of polyoxometalate‐catalyzed CO₂ coupling reactions. The reaction occurs through a single‐electron transfer from the doublet Co^II catalyst to the epoxide and forms a doublet Co^III–carbon radical intermediate. Subsequent CO₂ addition forms the cyclic carbonate product. The existence of radical intermediates is supported by free‐radical termination experiments. Finally, it is exhilarating to observe that the calculated overall reaction barrier (30.5 kcal mol^?1) is in good agreement with the real reaction rate (83 h^?1) determined in the present experiments (at 150 °C).     

Iron oxide on carbon‐based supports as efficient catalysts for organic compounds oxidation

For the first time, iron oxide on carbon aerogel, amine functionalized carbon nanotube, black carbon and carboxylic acid functionalized carbon nanotube in the presence of H₂O₂ was reported as an efficient and stable catalyst for the selective oxidation of sulfides and alcohols. The catalysts were characterized by scanning electron microscopy, energy‐dispersive spectroscopy, transmission electron microscopy, X‐ray photoelectron spectroscopy, X‐ray diffraction, Fourier transform infrared spectroscopy and atomic absorption spectroscopy. In the next step, catalytic reactivity toward sulfide to sulfoxide and alcohol to aldehyde/ketone oxidation in the presence of H₂O₂ was studied and discussed.     

Two‐Dimensional Spatial Resolution of Concentration Profiles in Catalytic Reactors by Planar Laser‐Induced Fluorescence: NO Reduction over Diesel Oxidation Catalysts

Planar laser‐induced fluorescence (PLIF) enables noninvasive in situ investigations of catalytic flow reactors. The method is based on the selective detection of two‐dimensional absolute concentration maps of conversion‐relevant species in the surrounding gas phase inside a catalytic channel. Exemplarily, the catalytic reduction of NO with hydrogen (2 NO+5 H₂→2 H₂O+2 NH₃) is investigated over a Pt/Al₂O₃ coated diesel oxidation catalyst by NO PLIF inside an optically accessible channel reactor. Quenching‐corrected 2D concentration maps of the NO fluorescence above the catalytic surface are obtained under both, nonreactive and reactive conditions. The impact of varying feed concentration, temperature, and flow velocities on NO concentration profiles are investigated in steady state. The technique presented has a high potential for a better understanding of interactions of mass transfer and surface kinetics in heterogeneously catalyzed gas‐phase reactions.     

Photoassisted Catalytic Oxidation of Carbon Monoxide at Room Temperature

Summary. The thermal and photoassisted catalytic oxidation of CO at metal oxide supported RuO₂·xH₂O was studied at room temperature. Contrary to neat RuO₂·xH₂O the supported catalysts suffer from fast deactivation attributed to strong adsorption of the reaction product carbon dioxide. The latter can be efficiently removed from the catalyst surface at elevated temperatures. In some cases, i.e. for catalysts supported with selected n-type semiconductors (TiO₂, SnO₂, WO₃), efficient CO₂ desorption and good, constant catalytic activity was observed upon visible light irradiation. Under such conditions the CO to CO₂ conversion observed for RuO₂·xH₂O/TiO₂ was nearly as good and stable as for the unsupported catalyst. It is suggested that light absorption promotes carbon dioxide desorption through positive charging of the catalyst surface.     

Rational Design of Crystalline Covalent Organic Frameworks for Efficient CO2 Photoreduction with H2O

Solar energy‐driven conversion of CO₂ into fuels with H₂O as a sacrificial agent is a challenging research field in photosynthesis. Herein, a series of crystalline porphyrin‐tetrathiafulvalene covalent organic frameworks (COFs) are synthesized and used as photocatalysts for reducing CO₂ with H₂O, in the absence of additional photosensitizer, sacrificial agents, and noble metal co‐catalysts. The effective photogenerated electrons transfer from tetrathiafulvalene to porphyrin by covalent bonding, resulting in the separated electrons and holes, respectively, for CO₂ reduction and H₂O oxidation. By adjusting the band structures of TTCOFs, TTCOF‐Zn achieved the highest photocatalytic CO production of 12.33 μmol with circa 100 % selectivity, along with H₂O oxidation to O₂. Furthermore, DFT calculations combined with a crystal structure model confirmed the structure–function relationship. Our work provides a new sight for designing more efficient artificial crystalline photocatalysts.     

Hydrogen Sulfide Induced Carbon Dioxide Activation by Metal‐Free Dual Catalysis

The role of metal free dual catalysis in the hydrogen sulfide (H₂S)‐induced activation of carbon dioxide (CO₂) and subsequent decomposition of resulting monothiolcarbonic acid in the gas phase has been explored. The results suggest that substituted amines and monocarboxylic type organic or inorganic acids via dual activation mechanisms promote both activation and decomposition reactions, implying that the judicious selection of a dual catalyst is crucial to the efficient C?S bond formation via CO₂ activation. Considering that our results also suggest a new mechanism for the formation of carbonyl sulfide from CO₂ and H₂S, these new insights may help in better understanding the coupling between the carbon and sulfur cycles in the atmospheres of Earth and Venus.     

Catalytic properties of the VO<Subscript><Emphasis Type="Italic">х</Emphasis></Subscript>/Ce<Subscript>0.46</Subscript>Zr<Subscript>0.54</Subscript>O<Subscript>2</Subscript> oxide system in the oxidative dehydrogenation of propane

Ce_0.46Zr_0.54O₂ solid solution prepared using a cellulose template was employed as a carrier for vanadium catalysts of the oxidative dehydrogenation of propane. The properties of VO _х /Ce_0.46Zr_0.54O₂ catalyst (5 wt % vanadium) are compared with the properties of the neat support. The carrier and catalyst are studied by means of BET, SEM, DTA, XRD, and Raman spectroscopy. It is shown that the CeVO₄ phase responsible for the ODH process is formed upon interaction between vanadate ions and cerium ions on the surface of the solid solution. The catalytic properties of the catalyst and the support are studied in the propane oxidation reaction at temperatures of 450 and 500°C with pulse feeding of the reagent. It is found that the complete oxidation of propane occurs on the support with formation of CO₂ and H₂O. Three products (propene, CO₂, and H₂O) form in the presence of the vanadium catalyst. It is suggested that there are two types of catalytic centers on the catalyst’s surface. It is concluded that the centers responsible for the complete oxidation of propane are concentrated mainly on the carrier, while the centers responsible for propane ODH are on the CeVO₄.     

Surface Engineering of g‐C3N4 by Stacked BiOBr Sheets Rich in Oxygen Vacancies for Boosting Photocatalytic Performance

BiOBr containing surface oxygen vacancies (OVs) was prepared by a simple solvothermal method and combined with graphitic carbon nitride (g‐C₃N₄) to construct a heterojunction for photocatalytic oxidation of nitric oxide (NO) and reduction of carbon dioxide (CO₂). The formation of the heterojunction enhanced the transfer and separation efficiency of photogenerated carriers. Furthermore, the surface OVs sufficiently exposed catalytically active sites, and enabled capture of photoexcited electrons at the surface of the catalyst. Internal recombination of photogenerated charges was also limited, which contributed to generation of more active oxygen for NO oxidation. Heterojunction and OVs worked together to form a spatial conductive network framework, which achieved 63 % NO removal, 96 % selectivity for carbonaceous products (that is, CO and CH₄). The stability of the catalyst was confirmed by cycling experiments and X‐ray diffraction and transmission electron microscopy after NO removal.