Promotional effects of Sb on Pd-based catalysts for the direct synthesis of hydrogen peroxide at ambient pressure

TiO2‐supported Pd‐Sb bimetallic catalysts were prepared and evaluated for the direct synthesis of H2O2 at ambient pressure.The addition of Sb to Pd significantly enhanced catalytic performance,and a Pd50Sb catalyst showed the greatest selectivity of up to 73%.Sb promoted the dispersion of Pd on TiO2,as evidenced by transmission electron microscopy and X‐ray diffraction.X‐ray photoelectron spectroscopy indicated that the oxidation of Pd was suppressed by Sb.In addition,Sb2O3 layers were formed and partially wrapped the surfaces of Pd catalysts,thus suppressing the activation of H2 and subsequent hydrogenation of H2O2.In situ diffuse reflection infrared Fourier transform spectroscopy for CO adsorption suggested that Sb homogenously located on the surface of Pd‐Sb catalysts and isolated contiguous Pd sites,resulting in the rise of the ratio of Pd monomer sites that are favorable for H2O2 formation.As a result,the Sb modified Pd surfaces significantly enhanced the non‐dissociative activation of O2 and H2O2 selectivity.

Heterogeneous interfacial engineering of Pd/TiO2 with controllable carbon content for improved direct synthesis efficiency of H2O2

Series of heterogeneous interfacial engineered TiO2(C-TiO2) with controllable carbon content were facilely synthesized by incipient-wet impregnation using glucose and subsequent thermal carbonization. The obtained C-TiO2 were used as catalytic supports to load Pd nanoparticles for H2 O2 direct synthesis from H2 and O2. The as-prepared samples were systematically studied by transmission electron microscopy(TEM), X-ray photoelectron spectroscopy(XPS), air isothermal microcalorimeter, temperature-programmed reduction of H2(H2-TPR), and so on. The catalytic results showed that H2 O2 productivity and H2O2 selectivity of Pd/C-TiO2 firstly rose with increasing carbon content and then declined. Pd/C-TiO2 catalyst with 1.89 wt% of carbon content showed the best catalytic performance that had 61.2% of selectivity and 2192 mmol H2O2/g Pd/h of productivity, which were significantly better than those of pristine Pd/TiO2(45.2% and 1827 mmol H2O2/g Pd/h). Various characterization results displayed that the carbon species were heterogeneously dispersed on TiO2 surface. Moreover, no obvious geometric transformation in supports and Pd nanoparticles were observed among different catalysts. The superficial hydrophobicity of Pd/C-TiO2 was gradually promoted with increasing carbon content, which led to the corresponding decrease in adsorption energy of H2O2 with catalysts. According to structure-performance relationship analyses, the heterogeneous interfacial engineering of carbon could maintain the interaction of Pd nanoparticles with TiO2 and simultaneously accelerate the H2O2 desorption. Both factors further determined the excellent H2O2 direct synthesis performance of Pd/C-TiO2.

Direct synthesis of hydrogen peroxide over Pd nanoparticles embedded between HZSM-5 nanosheets layers

Direct synthesis of hydrogen peroxide(DSHP)was studied over Pd loaded on HZSM-5 nanosheets(Pd/ZN).Pd nanoparticles with average size of ca.4.3 nm were introduced into the adjacent nanosheet layers(thickness of ca.2.9 nm)by impregnation method.Pd/ZN with theoretical Si/Al molar ratio of 25 showed the highest selectivity for H2O2 among the prepared catalysts,together with highest formation rate of H2O2(38.0 mmol·(g cat)^-1·h^-1),1.9 times than that of Pd supported on conventional HZSM-5 zeolite(Pd/CZ-50).Better catalytic performance of nanosheet catalysts was attributed to the promoted Pd dispersion which promoted H2 dissociation,more BrΦnsted acid sites and stronger metal-support interaction which inhibited the dissociation of O-O bond in H2O2.The embedded structure sufficiently protected the Pd nanoparticles by space confinement which restrained the Pd leaching,leading to a better catalytic stability with 90%activity retained after 3 cycles,which was almost 3 times than that of Pd/CZ-50(30.4%activity retained).

A Bi-component Cu Catalyst for the Direct Synthesis of Methylchlorosilane from Silicon and Methyl Chloride

A bi-component catalyst comprising CuC1 and metallic copper was used in the direct synthesis of me- thylchlorosilane to study the catalytic synergy between the different copper sources. The catalyst exhibited high ac- tivity and high selectivity of dimethyldichlorosilane （M2） in the stirred bed reactor. The effect of the proportion of CuC1 used was studied and 10%-30% CuC1 gave the best yield of M2. The use of CuC1 decreased the induction pe- riod of reaction, improved the selectivity in the induction stage, and gave a longer stable stage. These results sug- gest that bi-comoonent catalyst has advantazes in the direct synthesis reaction.

A review on direct synthesis of dimethoxymethane

Polyoxymethylene dimethyl ethers are recognized as the prospective diesel additive to decrease the pollutant emission from the light-duty vehicles,which can be polymerize form the monomer of dimethoxymethane(DMM).The industrial synthesis of DMM is mainly involved two-step process:methanol is oxidized to form the formaldehyde in fixed bed reactor and then reacted with the generated formaldehyde through acetalization in continuous stirred-tank reactor.Due to huge energy consumption,this typical synthesis route of DMM needs to be upgraded and more green routes should be determined.In this review,four state-of-the-art one-step direct synthetic routes,including two upgrading routes(methanol direct oxidation and direct dehydrogenation)and two green routes(methanol diethyl ether direct oxidation and carbon oxides direct hydrogenation),have been summarized and compared.Combination with the reaction mechanism and catalytic performance on the different catalysts,the challenges and opportu nities for every synthetic route are proposed.The relationships between catalyst structu re and property in different synthesis strategy are also investigated and then the suggestions of the design of catalyst are given about future research directions that efforts should be made in.Hopefully,this review can bridge the gap between newly developed catalysts and synthesis technology to realize their commercial applications in the near future.

A first-principles study of reaction mechanism over carbon decorated oxygen-deficient TiO_(2) supported Pd catalyst in direct synthesis of H_(2)O_(2)

The choice of support is one of the most significant components in the direct synthesis of H_(2)O_(2).Aiming to improvement of activity and selectivity of H_(2)O_(2) on Pd/TiO_(2) surface,we systematically investigated the important elementary steps on Pd/TiO_(2)-Vo@C,Pd/TiO_(2)-Vo,Pd/TiO_(2)-2 Vo,Pd/TiO_(2),and Pd/C using the first-principles calculations.The Bader charge analysis and charge density difference of O_(2) adsorption elucidate the relationship between the electronic distribution and chemisorption energy.The effective barrier analysis further enables to quantitatively estimate the reactivity of H_(2)O_(2) and H2O.We demonstrate unambiguously that the selectivity of H2O formation is boosted as the oxygen vacancy concentration raised.Moreover,the introduction of C into a TiO_(2) with appropriate oxygen vacancies can slightly reduce the effective barrier for H_(2)O_(2) formation and increase the effective barrier for H2O formation leading to a higher activity and selectivity of H_(2)O_(2) formation.Our finding suggests that carbon-doped oxygen vacancy TiO_(2) supported Pd is potential alternative catalyst compared with the Pd/TiO_(2).

High Activity and Selectivity of Cu/SiO_2 Catalyst for the Direct Synthesis of Indole

Copper supported over silica exhibited very high activity and selectivity for the direct synthesis of indole at atmospheric pressure. Under the reaction temperature of 325C,the yield of indole could obtain 88%.

Direct synthesis of single-phase α-CaSO4·0.5H2O whiskers from waste nitrate solution

Single-phaseα-CaSO4·0.5H2O whiskers were directly synthesized from waste Ca(NO3)2 solution using a hydrothermal method,and HNO3 was synchronously regenerated.The effects of reaction temperature and Ca^2+concentration on the phase composition and morphology of products were determined by X-ray diffraction and optical microscopy.On the basis of the experimental results,the formation diagram ofα-CaSO4·0.5H2O was plotted within the range of 5–35 g·L^-1 Ca^2+and 115°C–150°C.In addition,the conditions of the direct synthesis ofα-CaSO4·0.5H2O were determined.Well-crystallized,single-phaseα-CaSO4·0.5H2O whiskers with high aspect ratios(length,1785μm;diameter,10.63μm;aspect ratio,168)and HNO3(70.25 g·L^-1)were obtained at the optimal conditions of 25 g·L^-1 Ca^2+and 125°C.

Role of size and pretreatment of Pd particles on their behaviour in the direct synthesis of H_2O_2

Two families of catalysts, based on Pd nanoparticles supported on ceramic asymmetric tubular alumina membranes, are studies in the direct synthesis of H2O2. They are prepared by depositing Pd in two ways：（i） reduction with N2H4 in an ultrasonic bath and（ii） by impregnation-deposition. The first preparation leads to larger particles, with average size of around 11 nm, while the second preparation leads to smaller particles, with average size around 4 nm. The catalytic membranes were tested as prepared, after thermal treatment in air and after further pre-reduction with H2 in mild（100 ℃） conditions. Samples were characterized by TEM, CO-chemisorption monitored by DRIFTS method and TPR, while catalytic tests have been performed in a semi-batch recirculation membrane reactor. Experimental catalytic results were analysed using two kinetics models to derive the reaction constants for the parallel and consecutive reactions of the kinetic network. Smaller particles of Pd show lower selectivity due to the higher rate of parallel combustion, even if the better dispersion of Pd and thus higher metal surface area in the sample lead to a productivity in H2O2 similar or even higher than the sample with the larger Pd particles. Independently on the presence of smaller or larger Pd nanoparticles, an oxidation treatment leads to a significant enhancement in the productivity, although the catalyst progressively reduces during the catalytic process. The inhibition of the parallel combustion reaction（to water） induced from the calcination treatment remains after the in-situ reduction of the oxidized Pd species formed during the pre-treatment.This is likely due to the elimination of defect sites which dissociatively activate oxygen, and tentatively attributed to Pd sites able to give three- and four-fold coordination of CO.

Low Temperature Direct Synthesis of Strontium Titanate Powder

Low temperature direct synthesis (LTDS) involves the preparation of a base solution of Sr^(2+),and the mixing of base solution with tetrabutyl titanate solution.LTDS is an advantageous method because it does not require the complex hydrothermal facilities and it can prevent the agglomeration in calcinations of other liquid methods.In our work,we adopted LTDS method to prepare the nano strontium titanate powders,and characterize them by XRD,FT-IR and TGA.The influences of preparation temperature and solvents on grain size and lattice parameters were investigated.The results show that preparation temperature can slightly change the lattice parameters of grain,while solvents also play important roles in the preparation.

DIRECT SYNTHESIS OF SIA LON/ SiC MULTIPHASE REF RACTORY USING CLAY

Sialon/ Si C m ultiphase refractory w as directly synthesized using cheap clay , Si C particlesand proper ad ditives . The new synthesizing process is si m ple an d of low cost . The synthesizedm aterial has good roo m tem perature m echanical properties and ther m al shock resistance . Thisw ork has provided the experi mental basis for the ap plication of high property an d cheap Sialon/ Si C m ultiphase refractories .

BrCo (dmgh)_2Py/Zn Promoted Addition of BrCF_2CF_2CH=CHCH_2X to Alkynes: Direct Synthesis of 4,4,5,5-Tetrafluorocyclopentene Derivatives

BrCF2CF2CH=CHCH2X(x=Cl, OAc, OH) reacted smoothly with alkynes in the presence of BrCo(dmgh)2Py/Zn, giving 4,4,5,5-tetrafluorocyclopentene derivatives in moderate yields.

Direct Synthesis of Graphene on Silicon at Low Temperature for Schottky Junction Solar Cells

Graphene thin films synthesized directly at low temperature (550˚C) on silicon substrate by microwave (MW) surface wave plasma (SWP) chemical vapor deposition (CVD) using the cover on substrates for avoiding plasma emission ultraviolet ray’s effect during film deposition. Analytical methods such as Raman spectroscopy, Transmission electron microscopy (TEM) and Scanning electron microscopy (SEM), four-point probe method, and JASCO V-570 UV/VIS/NIR spectrophotometer were employed to characterize the properties of the graphene films. Here, we report that it is possible to grow graphene directly on the silicon substrate (without using catalyst) due to the high radical density of MW SWP CVD. Furthermore, we fabricated graphene/silicon Schottky junction solar cells with an efficiency of up to 6.39%. Compared to conventional silicon solar cells, the fabrication process is greatly simplified;just graphene is synthesized directly on n-type crystalline Si substrate at low temperate.

Pd catalysts supported on rGO-TiO_2 composites for direct synthesis of H_2O_2: Modification of Pd^(2+)/Pd^0 ratio and hydrophilic property

The use of nanostructured composites as catalyst supports is a promising route to prepare catalysts with high selectivity and productivity. In this work, reduced graphene oxide-TiO_2(rGP-x) composites with a variation of reduced graphene oxide(rGO) content were synthesized by hydrothermal method. Pd/rGP-x catalysts were prepared in incipient-wetness impregnation method for the direct synthesis of H_2O_2 from H2 and O_2. The morphology and electronic properties of catalysts were investigated by XPS, TEM, and Raman spectroscopy.The ratio of Pd^(2+)/Pd^0 and the hydrophobicity of the catalysts were increased with the rising content of rGO. As the amount of rGO in the catalysts varied in the range of 0.025 wt%–2 wt%, the selectivity of H_2O_2 exhibited a tendency of increasing firstly and then decreasing from 0.1 wt% to 2 wt%. It indicates that good catalytic performance for H_2O_2 synthesis can be achieved only when appropriate amount of rGO is introduced. The H_2O_2 selectivity and productivity of Pd/r GP-0.025 both improved remarkably compared with Pd/P25. This enhancement originated from the combined effects of the proper ratio of Pd^(2+)/Pd^0 and hydrophobicity of the catalyst.

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.

Direct synthesis of highly conductive poly（3,4- ethylenedioxythiophene）：poly（4-styrenesulfonate） （PEDOT：PSS）/graphene composites and their applications in energy harvesting systems

We report for the first time highly conductive poly（3,4-ethylenedioxythiophene）： poly（4-styrenesulfonate） （PEDOT：PSS）/graphene composites fabricated by in situ polymerization and their applications in a thermoelectric device and a platinum （Pt）-free dye-sensitized solar cell （DSSC） as energy harvesting systems. Graphene was dispersed in a solution of poly（4-styrenesulfonate） （PSS） and polymerization was directly carried out by addition of 3,4-ethylenedioxythiophene （EDOT） monomer to the dispersion. The content of the graphene was varied and optimized to give the highest electrical conductivity. The composite solution was ready to use without any reduction process because reduced graphene oxide was used. The fabricated film had a conductivity of 637 S.cm-1, corresponding to an enhancement of 41%, after the introduction of 3 wt.% graphene without any further complicated reduction processes of graphene being required. The highly conductive composite films were employed in an organic thermoelectric device, and the device showed a power factor of 45.7 μW·m^-1K^-2 which is 93% higher than a device based on pristine PEDOT：PSS. In addition, the highly conductive composite films were used in Pt-free DSSCs, showing an energy conversion efficiency of 5.4%, which is 21% higher than that of a DSSC based on PEDOT：PSS.

Studies on the Mechanism of the Direct Synthesis of Styrene form Benzene and Ethylene

The adsorption behavior and description behavior of benzene , ethylene and ethylbenzene over HZSM-5 and Co/HZSM-5 catalysts were studied by means of TPSR (Temperature programmed surface reaction) technique. TPSR results of ben- zene and ethylene co-adsorption show that the maian products are styrene , ethylben- zene, toluene, propane, and butane. In a separate experiment of ethylbenzene ad- sorption, styrene . toluene and benzene are formed due to cracking and dehydro- genation. The mechanism of styrene formation was proposed , i. e. , the reaction was carried out via. the dehydrogenation of mediate species ethylbenzene according to the results of TPSR-MS , activity testing and thermodynamic analysis.

Enhanced performance in the direct electrocatalytic synthesis of ammonia from N2 and H2O by an in-situ electrochemical activation of CNT-supported iron oxide nanoparticles

The direct electrocatalytic synthesis of ammonia from N2 and H2O by using renewable energy sources and ambient pressure/temperature operations is a breakthrough technology,which can reduce by over 90%the greenhouse gas emissions of this chemical and energy storage process.We report here an in-situ electrochemical activation method to prepare Fe2O3-CNT(iron oxide on carbon nanotubes)electrocatalysts for the direct ammonia synthesis from N2 and H2O.The in-situ electrochemical activation leads to a large increase of the ammonia formation rate and Faradaic efficiency which reach the surprising high values of 41.6μg mgcat^−1 h^−1 and 17%,respectively,for an in-situ activation of 3 h,among the highest values reported so far for non-precious metal catalysts that use a continuous-flow polymer-electrolytemembrane cell and gas-phase operations for the ammonia synthesis hemicell.The electrocatalyst was stable at least 12 h at the working conditions.Tests by switching N2 to Ar evidence that ammonia was formed from the gas-phase nitrogen.The analysis of the changes of reactivity and of the electrocatalyst characteristics as a function of the time of activation indicates a linear relationship between the ammonia formation rate and a specific XPS(X-ray-photoelectron spectroscopy)oxygen signal related to O2−in iron-oxide species.This results together with characterization data by TEM and XRD suggest that the iron species active in the direct and selective synthesis of ammonia is a maghemite-type iron oxide,and this transformation from the initial hematite is responsible for the in-situ enhancement of 3-4 times of the TOF(turnover frequency)and NH3 Faradaic efficiency.This transformation is likely related to the stabilization of the maghemite species at CNT defect sites,although for longer times of preactivation a sintering occurs with a loss of performances.

Direct synthesis of Fe-Si-B-C-Cu nanocrystalline alloys with superior soft magnetic properties and ductile by melt-spinning

Structure,magnetic properties and ductile of melt-spun Fe_(83-x)Si_(4)B_(13-y)C_(y)Cu_(x)(x=0-1.7;y=0-8)alloys were investigated.The addition of 1.7 at.%Cu in a Fe_(83)Si_(4)B_(13) amorphous alloy generates abundantα-Fe crystals by providing nucleation sites,and further C doping promotes the growth of the crystals by suitable turning amorphous-forming ability,hence they increase saturation magnetic flux density(B_(s))and slightly worse magnetic softness of the as-spun alloys.The as-spun Fe_(81.3)Si_(4)B_(7)C_(6)Cu_(1.7) alloy possesses a combined structure of a fully amorphous layer in wheel side surface and predominating nanocrystalline structure with gradually enlargedα-Fe crystal,whose average size and volume fraction are determined as about 12 nm and 32%,respectively,therefore superior soft magnetic properties and ductile with a high B_(s)of 1.74 T,coercivity(H_(c))of 32.7 A/m,effective permeability(μ_(e),at 1 kHz)of 3200 and high relatively strain at fracture(ε_(f))of 3.61%can be achieved directly in this alloy by only using melt-spinning.The annealing at 578 K releases internal stress,promotes the growth of theα-Fe crystals and remains the amorphous layer of the Fe_(81.3)Si_(4)B_(7)C_(6)Cu_(1.7) alloy,then improves the soft magnetic properties and maintains the superior ductile with increasing the B_(s)andμ_(e)to 1.80 T and 14,100,respectively,lowering the H_(c)to9.4 A/m and slightly reducing theε_(f)to 2.39%.The combination of superior soft magnetic properties and ductile and simplified synthesis process entitles the Fe-Si-B-C-Cu nanocrystalline alloys great potentials in high performance electromagnetic applications.

Study of Synthesis of Copoly (lactic acid/glycolic acid) by Direct Melt Polycondensation

A two steps direct copolymerisation process was developed. The first step is to produce oligomer and then the oligomer of lactic acid/glycolic acid (90/10) is polymerized with binary catalyst tin chloride dihydrate/p-toluenesulfonic acid. In this way, the direct synthesis of copoly (lactic acid/glycolic acid) without any organic solvent was investigated. The properties and structures of products were characterized by nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), X-ray diffraction and so on. The results show that comparatively high molecular weight copolymer of lactic acid and glycolic acid can be prepared by direct processing under appropriate technological conditions.