Molybdenum tailored Co^(0)/Co^(2+)active pairs on a perovskite-type oxide for direct ethanol synthesis from syngas

Selective synthesis of ethanol from syngas under the Co-based catalysts is still challenging due to the hard of regulating the active site Co^(0) and Co^(2+)ratio.In this work,a series of CaTi_(0.9-x)Co_(x)Mo_(0.1)O_(3)(x=0,0.1-0.4)and CaTi_(0.7)Co_(0.3)O_(3) catalysts were prepared by using citric acid complexation method to promote the synthesis of ethanol.It was found that Mo species in the perovskite lattice can regulate the Co^(0) and Co^(2+)ratio through the domain-limiting effect of perovskite and the degree of Co reduction could be adjusted by changing the Co/Mo molar ratio.Among these investigated catalysts,the total selectivity of alcohols over the catalyst with the optimal Co/Mo ratio CaTi_(0.6)Co_(0.3)Mo_(0.1)O_(3) reached 39.1%,with ethanol accounting for 74.7%,which was ascribed to the moderate and tightly bound ratio of dissociative to non-dissociative adsorption sites on the surface and the balance of CH_(x)-CH_(y) coupling and C^(O) insertion.

Facile Synthesis of Rose-Like NiO Nanoparticles and Their Ethanol Gas-Sensing Property

In this study, rose-like nickel oxide （NiO） nanoparticles with diameters of 400-500 nm are prepared on ITO glass substrates by simple electrodeposition in NiSO46H20 solution at room temperature followed by oxidation in air. Scanning electron microscopy, x-ray diffraction and a transmission electron microscope are used for analyses of the NiO nanoparticles. The ethanol gas sensitivity of these nanoparticles is studied. The results indicate that the rose-like NiO nanoparticles could be used for the fabrication of ethanol gas sensors to monitor the low concentration of ethanol gas in air. Furthermore, at 5 ppm, the NiO nanorose-based sensors show a high response to ethanol （Rg/Ra = 8.4）.

A highly selective catalyst of Co/La_(4)Ga_(2)O_(9) for CO_(2) hydrogenation to ethanol

A new catalyst of Co/La_(4)Ga_(2)O_(9) for CO_(2) hydrogenation to produce ethanol was prepared by reducing LaCo^(0).5 Ga0.5 O3,which showed excellent selectivity to ethanol(%35 C-mol%)at mild reaction conditions(270°C,3.5 MPa,3000 m L g-1 h-1).The catalysts were characterized by N_(2) adsorption/desorption,XRD,XAFS,CO and CO_(2)-TPD,H2 chemisorption,XPS and TEM techniques.The interaction between Co nanoparticles(NPs)and La2+4 Ga_(2)O_(9) oxide resulted in Co^(0)-Coon the surface of Co NPs.It was proposed that La_(4)Ga_(2)O_(9) could catalyze reverse water gas shift reaction(r-WGS),which converted CO_(2) to CO.Then,the CO migrated to Co^(0)-Co^(2+)on Co NPs,where it was hydrogenated to form ethanol like higher alcohols synthesis from syngas.The results suggest that by controlling the oxidation state of cobalt,and combined with a kind of active site for activating CO_(2) to form CO,a catalyst with excellent selectivity to ethanol could be obtained for CO_(2) hydrogenation,which means that the complex reaction may be proceed with high selectivity using only one active metal component.

Construction of bifunctional single-atom catalysts on the optimized β-Mo_(2)C surface for highly selective hydrogenation of CO_(2) into ethanol

Green and economical CO_(2)utilization is significant for CO_(2)emission reduction and energy development.Here,the 1D Mo_(2)C nanowires with dominant(101)crystal surfaces were modified by the deposition of atomic functional components Rh and K.While unmodifiedβMo_(2)C could only convert CO_(2)to methanol,the designed catalyst of K_(0.2)Rh_(0.2)/β-Mo_(2)C exhibited up to 72.1%of ethanol selectivity at 150℃.It was observed that the atomically dispersed Rh could form the bifunctional active centres with the active carrierβMo_(2)C with the synergistic effects to achieve highly specific controlled C–C coupling.By promoting the CO_(2)adsorption and activation,the introduction of an alkali metal(K)mainly regulated the balanced performance of the two active centres,which in turn improved the hydrogenation selectivity.Overall,the controlled modification ofβMo_(2)C provides a new design strategy for the highly efficient,lowtemperature hydrogenation of CO_(2)to ethanol with single-atom catalysts,which provides an excellent example for the rational design of the complex catalysts.

One-step conversion of methane and formaldehyde to ethanol over SA-FLP dual-active-site catalysts: A DFT study

One-step conversion of methane and formaldehyde into ethanol is a 100% atom-efficient process for carbon resources utilization and environment protection but still faces eminent challenges due to the lacking of efficient catalysts. Therefore, developing active and stable catalysts is crucial for the co-conversion of methane and formaldehyde. Herein, twelve kinds of “Single-Atom”-“Frustrated Lewis Pair”(SA-FLP)dual-active-site catalysts are designed for the direct conversion of methane and formaldehyde to ethanol based on density functional theory(DFT) calculations and microkinetic simulations. The results show that the SA-FLP dual active sites can simultaneously activate methane at the SA site and activate formaldehyde at the FLP site. Among the twelve designed SA-FLP catalysts, Fe1-FLP shows the best performance in the co-conversion of methane and formaldehyde to ethanol with the rate-determining barrier of 1.15 e V.Ethanol is proved as the main product with the turnover frequency of 1.32 × 10^(-4)s^(-1)at 573 K and 3 bar.This work provides a universal strategy to design dual active sites on metal oxide materials and offers new insights into the effective conversion of methane and formaldehyde to desired C_(2) chemicals.

The role of CO_(2)dissociation in CO_(2)hydrogenation to ethanol on CoCu/silica catalysts

CoCu-based catalysts are widely used in CO_(x) hydrogenation reactions to produce higher alcohols due to the C–C coupling ability of Co and the ability of Cu to produce alcohols.This work describes the role of easily happened CO_(2)dissociation on the CoCu surface during the reaction,using different silica support to tune the metal–support interaction,reaches different selectivity to ethanol.CoCu supported on mesoporous silica MCM-41 shows ethanol selectivity as high as 85.3%,the ethanol space-time yield(STY)is 0.229 mmol/(gmetal∙h),however,poor selectivity to ethanol as low as 28.8%is observed on CoCu supported on amorphous silica.The different selectivity is due to the different intensities of CO_(2)dissociation on the catalysts.The adsorbed O*produced via CO_(2)dissociation can occupy the cobalt hollow sites on CoCu surfaces,which are also the adsorption sites of C1 intermediates for further C–C coupling.

Efficient Synthesis of p-Hydroxyphenyl Ethanol from Hydrogenation of Methyl p-Hydroxyphenylacetate with CNTs-promoted Cu-Zr Catalyst

Hydrogenation of methyl p-hydroxyphenylacetate has been used for the synthesis of p-hydroxyphenyl ethanol.The reaction was catalyzed by Cu_(i)Zr_(j)-x%(mass fraction)carbon nanotubes(CNTs)catalysts.Incorporation of a minor amount of CNTs into Cu_(i)Zr_(j) oxide can visibly increase the catalytic activity for the synthesis of p-hydroxyphenyl ethanol.The yield of p-hydroxyphenyl ethanol reaches 94.2%over a co-precipitated catalyst of Cu_(3)Zr_(1) oxide with 11.0%CNTs.Its catalytic activity shows no obvious decrease after three cycles.This is much better than the CNT-free co-precipitated catalyst with a good yield of 81.1%,Cu_(3)Zr_(1)-0%CNTs.