The newly-assisted catalytic mechanism of surface hydroxyl species performed as the promoter in syngas-to-C2 species on the Cu-based bimetallic catalysts

In the conversion process of syngas-to-C_(2)species,the OH species are inevitably produced accompanying the production of key intermediates CH_(x)(x=1-3),traditionally,the function of surface OH species is generally accepted as the hydrogenating reactive species.This work for the first time proposed and confirmed the assisted catalytic mechanism of surface OH species that performed as the promoter for syngas-to-C_(2)species on Cu-based catalysts.DFT and microkinetic modeling results reveal that the produced OH species accompanying the intermediates CH_(x)production on the MCu(M=Co,Fe,Rh)catalysts can stably exist to form OH/MCu catalysts,on which the presence of surface OH species as the promoter not only presented better activity and selectivity toward CH_(x)(x=1-3)compared to MCu catalysts,but also significantly suppressed CH_(3)OH production,providing enough CH_(x)sources to favor the production of C_(2)hydrocarbons and oxygenates.Correspondingly,the electronic properties analysis revealed the essential relationship between the electronic feature of OH/MCu catalysts and catalytic performance,attributing to the unique electronic micro-environment of the catalysts under the interaction of surface OH species.This new mechanism is called as OH-assisted catalytic mechanism,which may be applied in the reaction systems related to the generation of OH species.

Spectroscopic study on variations in illite surface properties after acid-base titration

FT IR, Raman microscopy, XRD, 29 Si and 27 Al MAS NMR, were used to investigate changes in surface properties of a natural illite sample after acid base potentiometric titration. The characteristic XRD lines indicated the presence of surface Al Si complexes, preferable to Al(OH) 3 precipitates. In the microscopic Raman spectra, the vibration peaks of Si O and Al O bonds diminished as a result of treatment with acid, then increased after hydroxide back titration. The varied ratio of signal intensity between IV Al and VI Al species in 27 Al MAS NMR spectra, together with the stable BET surface area after acidimetric titration, suggested that edge faces and basal planes in the layer structure of illite participated in dissolution of structural components. The combined spectroscopic evidence demonstrated that the reactions between illite surfaces and acid leaching silicic acid and aluminum ions should be considered in the model description of surface acid base properties of the aqueous illite.

Origin and effect of surface oxygen-containing species on electrochemical CO or CO_(2) reduction reactions

Renewable-energy-powered electrochemical CO or CO_(2)reduction reactions(CO_(2)RR)provide one of the most promising strategies to upgrade CO_(2)to valuable products.In the past decade,the existence and the mechanistic role of oxygen-containing species,such as(sub)surface oxide,hydroxide and oxyhydroxide species,at the electrode–electrolyte interface under reductive conditions have emerged as a topic of acute discussion within the CO_(2)RR field.Oxide-derived Cu attracted the most attention,while other surfaces,including Au,Ag and Sn,were also widely investigated.This review identifies likely causes for contrasting results and views in the literature,summarizes possible oxygen sources for the interfacial oxygen-containing species at the CO_(2)RR conditions,and discusses potential roles these species could play in affecting the rate and product distribution.Finally,perspectives on future efforts to reveal the identity and role of oxygen-containing species in the CO_(2)RR are presented.

Characterization and catalytic performance of CeO_2-Co/SiO_2 catalyst for Fischer-Tropsch synthesis using nitrogen-diluted synthesis gas over a laboratory scale fixed-bed reactor

The surface species of CO hydrogenation on CeO2-Co/SiO2 catalyst were investigated using the techniques of temperature programmed reaction and transient response method. The results indicated that the formation of H2O and CO2 was the competitive reaction for the surface oxygen species, CH4 was produced via the hydrogenation of carbon species step by step, and C2 products were formed by the polymerization of surface-active carbon species （-CH2-）. Hydrogen assisted the dissociation of CO. The hydrogenation of surface carbon species was the rate-limiting step in the hydrogenation of CO over CeO2-Co/SiO2 catalyst. The investigation of total pressure, gas hourly space velocity （GHSV）, and product distribution using nitrogen-rich synthesis gas as feedstock over a laboratory scale fixed-bed reactor indicated that total pressure and GHSV had a significant effect on the catalytic performance of CeO2-Co/SiO2 catalyst. The removal of heat and control of the reaction temperature were extremely critical steps, which required lower GHSV and appropriate CO conversion to avoid the deactivation of the catalyst. The feedstock of nitrogen-rich synthesis gas was favorable to increase the conversion of CO, but there was a shift of product distribution toward the light hydrocarbon. The nitrogen-rich synthesis gas was feasible for F-T synthesis for the utilization of remote natural gas.

Effects of pretreatment and reduction on the Co/Al_2O_3 catalyst for CO hydrogenation

The purpose of this study was to investigate the effect of preadsorbed CO at different temperatures, calcination temperatures, the combined influence of reduction temperature and time, and pretreatment using hydrogen or syngas as reduction agents on the F-T synthesis （FTS） activity and selectivity of Co/Al2O3 catalyst. The reactivity of the carbon species at higher preadsorption temperature with H2 in TPSR decreased, whereas the carbon-containing species showed higher reactivity over Co/Al2O3 catalyst with low calcination temperature. This agreed well with the order of catalytic activity for F-T synthesis on this catalyst. The catalytic activity of the catalyst varied with reduction temperature and time remarkably. CODEX optimization gave an optimum reduction temperature of 756 K and reduction time of 6.2 h and estimated C5＋ yield perfectly. The pretreatment of Co/Al2O3 catalyst with different reduction agents （hydrogen or syngas） showed important influences on the catalytic performance. A high CO conversion and C5＋ yield were obtained on the catalyst reduced by hydrogen, whereas methane selectivity on the catalyst reduced by syngas was much higher than that on the catalyst reduced by hydrogen.

Catalytic oxidation of vinyl chloride over Co-Ce composite oxides derived from ZIF-67 template:Effect of cerium incorporation

Transition metal oxides are regarded as an economical and efficient catalytic alternate for catalytic oxidation of volatile organic compounds(VOCs)emissions.The morphological decoration and the incorporation of extrinsic metals were demonstrated to be effective strategies for achieving noticeable catalytic improvement.In this work,a novel Co-Ce composite oxides catalyst was obtained by the pyrolysis of ZIF-67 template with the impregnation of certain cerium cations(denoted as ZIF-CoCe).Compared with the reference Co-Ce composite oxides by the sol-gel(denoted as SG-CoCe)and physical mixing(denoted as MIX-CoCe)methods,ZIF-CoCe delivers significantly higher catalytic activity for vinyl chloride oxidation,which are demonstrated to be closely related with its superior redox capacity,more abundance of surface active Co^(3+)sites and adsorbed active oxygen species from oxygen vacancies.In addition,the unique cage-like morphological feature of the Co-based catalysts derived from ZIF-67 template plays a crucial function in kinetically facilitating the mass transfer of catalytic reaction and promoting the catalytic VC oxidation activity.With regard to in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTs)analysis,enol and carboxylic acid species are identified to be the key organic intermediates during catalytic vinyl chloride oxidation.

Structures and catalytic performances of Me/SAPO-34(Me=Mn,Ni,Co)catalysts for low-tem perature SCR of NO_x by ammonia

Me/SAPO-34(Me=Mn,Ni,Co)series of catalysts were prepared by a wetness impregnation method and investigated for the selective catalytic reduction of nitrogen oxides with ammonia(NH 3-SCR).Among them,Mn/SAPO-34 catalyst was found as the most promising candidate based on its superior low-temperature activity.The catalysts were characterized by X-ray diffraction(XRD),transmission electron microscopy images(TEM),nuclear magnetic resonance(NMR),X-ray photoelectron spectroscopy(XPS),temperature programmed reduction and desorption(TPR and TPD),and diffuse reflectance infrared Fourier transformed spectroscopy(DRIFTS)of NH_(3)/NO_(x)adsorption.Mn/SAPO-34 is obviously different from Ni/SAPO-34 and Co/SAPO-34 in the active species state and distribution.Surface MnO_(x)species which play an essential role in NO oxidation and NO_(2)adsorption,act as better active sites than nickel and cobalt mostly in the form of the aluminates and silicates.

Screening performance of methane activation over atomically dispersed metal catalysts on defective boron nitride monolayers:A density functional theory study

Methane(CH_(4))controllable activation is the key process for CH_(4)upgrading,which is sensitive to the surface oxygen species.The high thermal conductivity and superb thermal stability of the hexagonal boron nitride(h-BN)sheet makes a single transition metal atom doped hexagonal boron nitride monolayer(TM-BN)possible to be a promising material for catalyzing methane partial oxidation.The performances of 24 TM-BNs for CH_(4)activation are systematically investigated during the CH_(4)oxidation by means of first-principles computation.The calculation results unravel the periodic va riation trends for the stability of TM-BN,the adsorption strength and the kind of O_(2)species,and the resulting CH_(4)activation performance on TM-BNs.The formed peroxide O_(2)^(2-)of which the O-O bond could be broken and O-anions are found to be reactive oxygen species for CH_(4)activation under the mild conditions.It is found that the redox potential of TM center,including its valence electron number,coordination environment,and the work function of TM-BN,is the underlying reason for the formation of different oxygen species and the resulting activity for CH_(4)oxidative dehydrogenation.