Geometric effect promoted hydrotalcites catalysts towards aldol condensation reaction

In solid basic catalysis field,how to achieve optimized activity and desired stability through elaborate control over basic site properties remains a challenge.In this work,taking advantage of the structure memory effect of layered double hydroxides(LDHs),rehydrated Ca4 Al1-x Gax-LDHs and Ca4 Al1-x Inx-LDHs catalysts were prepared and applied in aldol condensation reaction that isobutyraldehyde(IBD)reacts with formaldehyde(FA)to obtain hydroxypivalaldehyde(HPA).Notably,the resulting re-Ca4 Al0.90Ga0.10-LDHs exhibits an extraordinarily-high catalytic activity(HPA yield:72%),which is to our best knowledge the highest level in this reaction.The weak Br?nsted basic site,7-coordinated Ca-OH group,which serves as an active site,catalyzes the condensation process and promotes the product desorption.Studies on structure-property correlations demonstrate that Ga as a structural promoter induces a moderate expansion of the laminate lattice,which results in a significant increase in the concentration of weak basic sites in re-Ca4Al0.90Ga0.10-LDHs,accounting for its high catalytic activity.This work illuminates that geometric structure of basic active sites can be tuned via introducing catalyst additive,which leads to a largely improved performance of hydrotalcite solid basic catalysts towards aldol condensation reaction.

MgFe hydrotalcites-derived layered structure iron molybdenum sulfide catalysts for eugenol hydrodeoxygenation to produce phenolic chemicals

Hydrodeoxygenation（HDO） is an effective alternative to produce value-added chemicals and liquid fuels by removing oxygen from lignin-derived compounds. Sulfide catalysts have been proved to have good activity for the HDO and particularly high selectivity to phenolic products. Herein, we presented a novel way to prepare the layered structure sulfide catalysts（MgFeMo-S） derived from MgFe hydrotalcites via the intercalation of Mo in consideration of the memory effect of the calcined hydrotalcite. By varying the Mg/Fe mole ratio, a series of MgFeMo-S catalysts were successfully prepared and characterized by nitrogen adsorption/desorption isotherms, X-ray diffraction（XRD）, transmission electron microscopy（TEM）,and inductively coupled plasma optical emission spectrometer（ICP-OES）. The characterization results indicated that the MgFeMo-S catalyst has retained the unique layered structure, which can facilitate uniform dispersion of the MoS2 species on both the surface and interlayer of the catalysts. For the HDO of eugenol, the Mg1Fe2Mo-S catalysts exhibited the best HDO activity among all the catalysts due to its higher active metal contents and larger pore size. The HDO conversion was 99.6% and the yield of phenolics was 63.7%, under 5 MPa initial H2 pressure（measured at RT） at 300 ℃ for 3 h. More importantly,MoS2 species deposited on the interlayer galleries in the MgFeMo-S catalysts resulted in dramatically superior HDO activity to MoS2/Mg1Fe2-S catalyst. Based on the mechanism investigation for eugenol, the HDO reaction route of eugenol under sulfide catalytic system has been proposed for the first time. Further applicability of the catalyst on HDO of more lignin-derived compounds was operated, which showed good HDO activity and selectivity to produce aromatic products.

Influence of the preparation method on the catalytic activity of Mg-Al hydrotalcites as solid base catalysts

Mg-Al hydrotalcites were synthesized using different preparation methods(a co-precipitation method, a urea method, and a simple one) to analyze their effect on the catalytic activity of these solid base catalysts. The method strongly affected the structure of their layers(e.g., the growth and stacking of the layers, and the type of intercalated anions) and, accordingly, their catalytic activity. The Mg-Al hydrotalcite prepared by co-precipitation showed the best catalytic performance in the isomerization of glucose into fructose, due to the small crystallite size and sand rose morphology enhancing the exposure of surface active sites to reactants.

Preparation and Characterization of Mg/Al/Fe Hydrotalcite with Superb Absorption Capacity toward Congo Red

Mg/Al/Fe layered double hydroxide(MAF-LDH1) was prepared by solvothermal method with the sodium dodecyl sulfate as the template, and the ethanol system was benefit to growth of sample. The nature in the resulting MAF-LDH was investigated by X-ray diffraction, field emission scanning electron microscopy, Fourier transformed infrared spectra, thermogravimetric analysis, and N2 adsorption-desorption.The morphology of MAF-LDH1 is petal-like with the size of 400-500 nm and the thickness about 10-20 nm. The adsorption performance of the samples was evaluated by absorption of the Congo red(CR) solutions. Compared with Mg/Al layered double hydroxide(MA-LDH), the maximum adsorption capacities of the MAF-LDH1 samples were 943.4 mg/g which was greatly enhanced. Furthermore, after seven cycling tests, the adsorption performance was still up to 90%. Theoretical calculation results revealed that the adsorption process was spontaneous and followed the pseudo-second-order kinetic model and Freundlich model. This work provides a promising alternative strategy to enhance the adsorptive properties of hydrotalcite-like materials.

“Intelligent” reforming catalysts:Trace noble metal-doped Ni/Mg(Al)O derived from hydrotalcites

Trace amounts of noble metal-doped Ni/Mg（AI）O catalysts were pre- pared starting from Mg-Al hydrotalcites （HTs） and tested in daily start-up and shut-down （DSS） operation of steam reforming （SR） of methane or partial oxidation （PO） of propane. Although Ni/Mg（Al）O catalysts prepared from Mg（Ni）-Al HT exhibited high and stable activity in stationary SR, PO and dry reforming of methane and propane, the Ni/Mg（Al）O catalysts were drastically deactivated due to Ni oxidation by steam as purge gas when they were applied in DSS SR of methane. Such deactivation was effectively suppressed by doping trace amounts of noble metal on the catalysts by using a ＂memory effect＂ of HTs. Moreover, the noble metal-doped Ni/Mg（Al）O catalysts exhibited ＂intelligent＂ catalytic behaviors, i.e., self-activation and self-regenerative activity, leading to high and sustainable activity during DSS operation. Pt was the most effective among noble metals tested. The self-activation occurred by the reduction of Ni2＋ in Mg（Ni,Al）O periclase to Ni^0 assisted by hydrogen spillover from Pt （or Pt-Ni alloy）. The self-regenerative activity was accomplished by self-redispersion of active Ni^0 particles due to a reversible reductionoxidation movement of Ni between the outside and the inside of the Mg（Al）O periclase crystal; surface Ni^0 was oxidized to Ni2＋ by steam and incorporated into Mg（Ni2＋,Al）O periclase, whereas the Ni2＋ in the periclase was reduced to Ni^0 by the hydrogen spillover and appeared as the fine Ni^0 particles on the catalyst surface. Further a ＂green＂ preparation of the Pt/Ni/[Mg3.sAl]O catalysts was accomplished starting from commercial Mg3.5-AI HT by calcination, followed by sequential impregnation of Ni and Pt.

Steam reforming of methane over Ni catalysts prepared from hydrotalcite-type precursors: Catalytic activity and reaction kinetics

Ni/Mg–Al catalysts derived from hydrotalcite-type precursors were prepared by a co-precipitation technique and applied to steam reforming of methane. By comparison with Ni/γ-Al2O3 and Ni/α-Al2O3 catalysts prepared by incipient wetness impregnation, the Ni/Mg–Al catalyst presented much higher activity as a result of higher specific surface area and better Ni dispersion. The Ni/Mg–Al catalyst with a Ni/Mg/Al molar ratio of 0.5:2.5:1 exhibited the highest activity for steam methane reforming and was selected for kinetic investigation. With external and internal diffusion limitations eliminated, kinetic experiments were carried out at atmospheric pressure and over a temperature range of 823–973 K. The results demonstrated that the overall conversion of CH4 and the conversion of CH4 to CO2were strongly influenced by reaction temperature, residence time of reactants as well as molar ratio of steam to methane. A classical Langmuir–Hinshelwood kinetic model proposed by Xu and Froment(1989)fitted the experimental data with excellent agreement. The estimated adsorption parameters were consistent thermodynamically.

Ni-Co/Mg-Al catalyst derived from hydrotalcite-like compound prepared by plasma for dry reforming of methane

Ni-Co bimetallic catalysts with different Ni/Co content were derived from cold plasma jet decomposition and reduction of hydrotalcite-like compounds containing Ni,Co,Mg and Al,and their catalytic performance was investigated with dry reforming of methane.Experimental results showed that the hydrotalcite-like precursors could be completely decomposed and partly reduced by cold plasma jet,and the Nicontained catalysts exhibited much higher activity than the catalyst without Ni.Especially,the catalyst with Ni/Co ratio of 8/2 achieved not only the highest conversions of 80.3%and 69.3%for CH4 and CO2,respectively,but also the best stability in 100 h testing.The catalysts were characterized by XRD,XPS,TEM and N2 adsorption techniques,and the results showed that the better performance of the 8Ni2Co bimetallic catalyst was attributed to its higher metal dispersion,smaller metal particle size,as well as the interaction effect between Ni and Co,which were brought by the special catalyst preparation method.

A new way to synthesize benzoin isopropyl ether on Cu-Fe-hydrotalcite

An efficient synthesis of benzoin isopropyl ether with benzaldehyde and propanol in the presence of heterogeneous recyclable Cu-Fe-hydrotalcite catalyst has been explored. Cu-Fe-hydrotalcite was firstly successfully synthesized over Jahn-Teller effect of Cu^2＋. The catalytic test result showed that Cu-Fe-hydrotalcite could be used as a good catalyst in the synthesis of benzoin isopropyl ether. The highest conversion of ben- zaldehyde was 59.7% and the selectivity of benzoin isopropyl ether was nearly 100%. By this new method, not only was the cyanide poisoning avoided, but also the synthesis of benzoin isopropyl ether could be completed in one step instead of traditional two steps with both condensation and etherification.

Hydrogen Production Performances via Steam Reforming over Hydrotalcite Derived Catalyst: A Sustainable Energy Production Review

The review outcome represents the optimum catalytic conditions for the production of hydrogen using hydrotalcite derived catalysts. It covers dry and steam reforming of methane, steam reforming of methanol and ethanol to hydrogen. The review also revealed the specific properties of hydrotalcite derived catalysts for the reactions. Among catalyst investigated, Ni & Fe promoted Al-Mg containing hydrotalcite catalyst perform best (99%) for dry reforming of methane at 250°C. For steam methane reforming, Ni containing ca-aluminates hydrotalcite catalyst act as the best (99%) at 550°C. Cu-supported Zn-Al-containing catalyst performs the best (99.98%) for steam reforming of methanol at 300°C whereas Cu impregnated Mg-Al containing hydrotalcite is the best (99%) for steam reforming of ethanol at 200°C - 600°C. It’s (HT) tunable and versatile textural and morphological properties showed excellent catalytic performances for different industrial processes and in sustainable hydrogen production.

Study on the Synthesis and Properties of PET Using Hydrotalcite as Catalyst

Poly(ethylene terephthalate)(PET)was synthesized by the in-situ polymerization method using layered double hydrotalcite(LDH)as the catalyst,and the thermal and flame retardation properties of PET were investigated as required.As identified by differential scanning calorimetry(DSC)and thermogravimetric(TGA)analysis,the crystallization rate and thermal degradation temperature of the as-prepared PET sample were enhanced compared with commercial PET sample.It was confirmed from the fire-resistant property study that the LDH can be used as an efficient flame-retardant besides functioning as a catalyst in the transesterification/polycondensation process for PET synthesis.

Chemoselective Transfer Hydrogenation of Cinnamaldehyde over Activated Charcoal Supported Pt/Fe3O4 Catalyst

A variety of spherical and structured activated charcoal supported Pt/Fe3O4 composites with an average particle size of ~100 nm have been synthesized by a self-assembly method using the difference of reduction potential between Pt （Ⅳ） and Fe （Ⅱ） precursors as driving force. The formed Fe3O4 nanoparticles （NPs） effectively prevent the aggregation of Pt nanocrystallites and promote the dispersion of Pt NPs on the surface of catalyst, which will be favorable for the exposure of Pt active sites for high-efficient adsorption and contact of substrate and hydrogen donor. The electron-enrichment state of Pt NPs donated by Fe304 nanocrystallites is corroborated by XPS measurement, which is responsible for promoting and activating the terminal C=O bond of adsorbed substrate via a vertical configuration. The experimental results show that the activated charcoal supported Pt/Fe3O4 catalyst exhibits 94.8% selectivity towards cinnamyl alcohol by the transfer hydrogenation of einnamaldehyde with Pt loading of 2.46% under the optimum conditions of 120 ℃ for 6 h, and 2-propanol as a hydrogen donor. Additionally, the present study demonstrates that a high-efficient and recyclable catalyst can be rapidly separated from the mixture due to its natural magnetism upon the application of magnetic field.

Fe_3O_4@UiO-66-NH_2 core–shell nanohybrid as stable heterogeneous catalyst for Knoevenagel condensation

separation is an attractive alternative to filtration or centrifugation for separating solid catalysts from a liquid phase, Here, core-shell Fe3O4@UiO-66-NH2 nanohybrids with well-defined structures were constructed by dispersing magnets in a dimethylformamide （DMF） solution con- taining two metal-organic framework （MOF） precursors, namely ZrCI4 and 2-aminobenzenetricar- boxylic acid. This method is simpler and more efficient than previously reported step-by-step method in which magnets were consecutively dispersed in DMF solutions each containing one MOF precursor, and the obtained Fe304@UiO-66-NH2 with three assembly cycles has a higher degree of crystallinity and porosiW. The core-shell Fe3O4@UiO-66-NH2 is highly active and selective in Knoevenagel condensations because of the bifunctionality of UiO-66-NH2 and better mass transfer in the nano-sized shells. It also has good recycling stability, and can be recovered magnetically and reused at least four times without significant loss of catalytic activity and framework integrity. The effects of substitution on the reactivity of benzaldehyde and of substrate size were also investigated.

Fe-Ca-Ce催化生物质热解制备富氢合成气——以山楂药渣为例

以山楂药渣作为原料,在固定床反应器中研究了热解温度和Fe、Fe-Ca、Fe-Ca-Ce催化剂及负载量对药渣热解的影响规律,并研究了浸渍法和共沉淀法对热解气体产率的影响.研究结果表明,热解温度从500℃升高至700℃,H_(2)由10.40 mL/g升高至27.64 mL/g,当Fe负载量为w=7%时,H_(2)产率由27.64 mL/g增加至46.16 mL/g,在Fe中引入Ca有效提高了H_(2)的产率,Ca的负载量增加至w=2.0%时,H_(2)产率增加至69.53 mL/g.采用共沉淀法制备Fe和Fe-Ca催化剂有利于降低CO_(2)产率,而在Fe-Ca中引入Ce后H_(2)产率从69.53 mL/g减少至50.18 mL/g.

Fe(HSO_4)_3:An efficient,heterogeneous and reusable catalyst for the synthesis of 14-aryl- or alkyl-14H-dibenzo[a,j]xanthenes

Fe（HSO4）3 has been used as an efficient and recyclable catalyst for the one-pot synthesis of 14-aryl- or alkyl-14Hdibenzo[aj]xanthene derivatives by the reaction of 2-naphtol and aldehydes. Different types of aromatic and aliphatic aldehydes are used in the reaction and in all cases the products were obtained in good to excellent yields.

Effect of La on Partial Oxidation of Ethanol to Hydrogen over Ni/Fe Catalysts

The partial oxidation of ethanol to hydrogen was investigated over Ni/Fe/La catalysts prepared by the co precipitation method. The effects of introduction of La promoter and the reaction temperature on the catalytic performance were studied. It was found that the introduction of La into Ni/Fe catalysts is helpful to increase the selectivity to hydrogen and the stability of the catalysts. The results of XRD and XPS characterization show that the structure of the catalyst was changed during the reaction. The existence of LaFeO 3 species is possibly the main reason of the increase of the catalyst stability.

Layered double hydroxide-like Mg_3Al_(1–x)Fe_x materials as supports for Ir catalysts: Promotional effects of Fe doping in selective hydrogenation of cinnamaldehyde

Supported Ir catalysts were prepared using layered double hydrotalcite‐like materials,such as Mg3Al1-xFex,containing Fe and Al species in varying amounts as supports.These Ir catalysts were applied for the selective hydrogenation of cinnamaldehyde(CAL).When x was changed from 0(Ir/Mg3Al)to 1(Ir/Mg3Fe),the rate of CAL hydrogenation reached a maximum at approximately x=0.25,while the selectivity to unsaturated alcohol,i.e.,cinnamyl alcohol,monotonously increased from 44.9%to 80.3%.Meanwhile,the size of the supported Ir particles did not change significantly with x,remaining at 1.7-0.2 nm,as determined by transmission electron microscopy.The chemical state of Ir and Fe species in the Ir/Mg3Al1-xFex catalysts was examined by temperature programmed reduction by H2 and X‐ray photoelectron spectroscopy.The surface of the supported Ir particles was also examined through the in‐situ diffuse reflectance infrared Fourier‐transform of a probe molecule of CO.On the basis of these characterization results,the effects of Fe doping to Mg3Al on the structural and catalytic properties of Ir particles in selective CAL hydrogenation were discussed.The significant factors are the electron transfer from Fe2+in the Mg3Al1–xFex support to the dispersed Ir particles and the surface geometry.

Synthesis of Ag/AgCl/Fe-S plasmonic catalyst for bisphenol A degradation in heterogeneous photo-Fenton system under visible light irradiation

A novel plasmonic photo‐Fenton catalyst of Ag/AgCl/Fe‐S was synthesized by ion exchange and photoreduction methods.The obtained catalyst was characterized by X‐ray diffraction,X‐ray photoelectron spectroscopy,scanning electron microscope imaging,and Brunauer‐Emmett‐Teller measurements.Moreover,the photocatalytic activity of Ag/AgCl/Fe‐S was investigated for its degradation activity towards bisphenol A(BPA)as target pollutant under visible light irradiation.The effects of H2O2concentration,pH value,illumination intensity,and catalyst dosage on BPA degradation were examined.Our results indicated that the Ag/AgCl material was successfully loaded onto Fe‐sepiolite and showed a high photocatalytic activity under illumination by visible light.Furthermore,active species capture experiments were performed to explore the photocatalytic mechanism of the Ag/AgCl/Fe‐S in this heterogeneous photo‐Fenton process,where the major active species included hydroxyl radicals(?OH)and holes(h+).

Preparation of Fe_2P/Al_2O_3 and FeP/Al_2O_3 catalysts for the hydrotreating reactions

A 60%Fe/Al_2O_3 catalyst was prepared by the co-precipitation method.It was reduced by H_2 to produce metallic Fe,which was then sulfided by CS_2 to Fe_(0.96) S and Fe_3S_4 or phosphided by triphenylphosphine(PPh3) in liquid phases to Fe2 P and Fe P.It was found that the iron sulfides(Fe0.96 S and Fe_3S_4) exhibited the low activity for the hydrodesulfurization(HDS) reactions.The HDS activity was also low on the Fe(metal)/Al_2O_3 and Fe_2 P/Al_2O_3 catalysts since they were converted into Fe0.96 S and Fe_3S_4 during the HDS reactions.In contrast,the FeP/Al_2O_3 was found to be stable and active for the HDS reactions.In particular,Fe P/Al_2O_3 possessed significantly smaller Fe P particles than Fe P/C,leading to the significant higher HDS activity of FeP/Al_2O_3 than Fe P/C.

Fe3O4 nanoparticles impregnated eggshell as a novel catalyst for enhanced biodiesel production

Biodiesel is a green fuel which can replace diesel while addressing various issues such as scarcity of hydrocarbon fuels and environmental pollution to an extent. The high production cost of biodiesel and the recovery of the catalyst after the transesterification process are the major challenges to be addressed in biodiesel production. In the present work, a cheap and promising solid base oxide catalyst was synthesized from chicken eggshell by calcination at 900 ℃ forming catalyst eggshells(CES) and was impregnated with the nanomagnetic material(Fe3O4) to obtain Fe3O4 loaded catalytic eggshell(CES–Fe3O4). Fe3O4 nanomaterials were synthesized by co-precipitation method and were loaded in catalytic eggshell by sonication, for better recovery of the catalyst after transesterification process. CES–Fe3O4 material was characterized by Thermogravimetric analysis, X-ray diffraction, Fourier transform infrared spectroscopy, a vibrating-sample magnetometer, Brunauer-Emmett-Teller, Dynamic light scattering, and Scanning electron microscopy. Biodiesel was synthesized by transesterification of Pongamia pinnata raw oil with 1:12 oil to methanol molar ratio and 2 wt% catalyst loading for 2 h at a temperature of 65 ℃ and yields were compared. The reusability of the catalyst was studied by the transesterification of the raw oil and its catalytic activity was found to be retained up to 7 cycles with a yield of 98%.

Fe基催化剂的酸性调控及其对加氢脱硫反应路径选择性的影响

以Fe作为主活性金属、Zn作为助活性金属,制备了Y型分子筛改性的Fe基加氢脱硫(HDS)催化剂。采用低温氮气物理吸附、X射线衍射(XRD)、氢气程序升温还原(H_(2)-TPR)、氨气程序升温脱附(NH_(3)-TPD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)和吡啶红外(Py-IR)等表征方法对改性前后Fe基催化剂的形貌、孔结构、分散性、还原性、电子缺陷结构以及酸性等变化进行了研究,并使用固定床反应器对Fe基催化剂的HDS性能进行了评价。结果表明,Y型分子筛的引入提供了Bronsted(B)酸中心,使得Fe基催化剂的脱硫率提高了10.7%-34.1%。同时,B酸中心提高了催化剂的直接脱硫(DDS)反应路径的选择性。此外,B酸中心在促进DDS反应路径选择性增加的同时,抑制了预加氢脱硫(HYD)反应路径中四氢二苯并噻吩(THDBT)和六氢二苯并噻吩(HHDBT)更进一步的深度加氢,从而在保证脱硫率提升的同时又降低了氢耗。其根本原因可能是Y型分子筛的引入增强了催化剂的酸性,特别是B酸中心和活性金属之间的相互作用促进了电子转移,从而调节了Fe物种的电子缺陷结构,进而提升了催化剂的HDS性能。