Among the synthesis techniques for graphene,chemical vapor deposition(CVD)enables the direct growth of graphene films on insulating substrates.Its advantages include uniform coverage,high quality,scalability,and compa...Among the synthesis techniques for graphene,chemical vapor deposition(CVD)enables the direct growth of graphene films on insulating substrates.Its advantages include uniform coverage,high quality,scalability,and compatibility with industrial processes.Graphene is chemically inert and has a zero-bandgap which poses a problem for its use as a functional layer,and nitrogen doping has become an important way to overcome this.Post-plasma treatment has been explored for the synthesis of nitrogen-doped graphene,but the procedures are intricate and not suitable for large-scale production.We report the direct synthesis of nitrogen-doped graphene on a 4-inch sapphire wafer by ethanol-assisted CVD employing pyridine as the carbon feedstock,where the nitrogen comes from the pyridine and the hydroxyl group in ethanol improves the quality of the graphene produced.Additionally,the types of nitrogen dopant produced and their effects on III-nitride epitaxy were also investigated,resulting in the successful illumination of LED devices.This work presents an effective synthesis strategy for the preparation of nitrogen-doped graphene,and provides a foundation for designing graphene functional layers in optoelectronic devices.展开更多
Dimethyl carbonate(DMC)has many excellent properties[1]and can be produced by many methods[2].The direct synthesis of DMC from CO_(2),CO_(2)+2CH_(3)OH==DMC+H_(2)O,has some advan-tages[3]as compared with other methods,...Dimethyl carbonate(DMC)has many excellent properties[1]and can be produced by many methods[2].The direct synthesis of DMC from CO_(2),CO_(2)+2CH_(3)OH==DMC+H_(2)O,has some advan-tages[3]as compared with other methods,but the conversion is very low because the reaction equilibrium is to the left and the reaction can only proceed under special conditions[4].展开更多
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 ...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.展开更多
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 ...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).展开更多
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...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.展开更多
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-T...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.展开更多
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-...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.展开更多
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 ...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.展开更多
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 investigate...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).展开更多
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%.
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+concentr...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.展开更多
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） reduct...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.展开更多
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 requi...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.展开更多
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 ...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 .展开更多
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.
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 em...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.展开更多
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...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.展开更多
The direct synthesis of semi-conductive quantum dot(QD)inks coordinated by inorganic ions in polar phases presents potential advantages such as low cost and scalability,making it an ideal approach for realizing QDs-ba...The direct synthesis of semi-conductive quantum dot(QD)inks coordinated by inorganic ions in polar phases presents potential advantages such as low cost and scalability,making it an ideal approach for realizing QDs-based optoelectronic applications.However,the weak repulsive forces between QDs coordinated by inorganic ions can easily lead to agglomeration,significantly limiting size control during the synthesis process.Distinct from the traditional high-temperature injection and low-temperature growth strategy used in the synthesis of QDs with long-chain organic ligands,we discover that low-temperature injection nucleation and high-temperature growth is an effective strategy to achieve controllable tuning of reactive monomers and ligand ions in the direct synthesis system of inorganic ion-liganded QD inks,which in turn realizes the scalable,low-cost,and direct synthesis of uniform and size-tunable short-wavelength infrared(SWIR)PbS QD inks.The yield of single synthesis can be more than 10 g.Compared with the traditional ligand exchange method,the yield is improved by nearly 3 times and the cost is reduced to 7 times.Finally,the solar cell devices fabricated using these PbS SWIR QD inks achieved a photovoltaic conversion efficiency of approaching 9%,confirming the excellent optoelectronic performance of the synthesized PbS QD materials.展开更多
Metal-organic frameworks(MOFs)have garnered widespread attention due to their designability and diversity[1].Customization has always been a pursuit of chemists and materials scientists[2].Topology provides a means of...Metal-organic frameworks(MOFs)have garnered widespread attention due to their designability and diversity[1].Customization has always been a pursuit of chemists and materials scientists[2].Topology provides a means of abstracting the complex structures of MOFs by identifying and classifying the fundamental building units and connection patterns,simplifying the understanding of MOF structures[3].展开更多
Hydrogen peroxide(H_(2)O_(2))is a green oxidant that has been widely used.The direct synthesis of hydrogen peroxide(DSHP)offers significant advantages in terms of high atomic economy and environmentally friendly effec...Hydrogen peroxide(H_(2)O_(2))is a green oxidant that has been widely used.The direct synthesis of hydrogen peroxide(DSHP)offers significant advantages in terms of high atomic economy and environmentally friendly effects.However,due to the inevitable side reactions and severe mass transfer limitations,it is still challenging to balance the selectivity and activity for the DSHP.Combining theoretical understanding with the controllable synthesis of nanocatalysts may significantly facilitate the design of“dream catalysts”for the DSHP.In this work,the main factors affecting the reaction performance of catalysts and the active sites of catalysts have been reviewed and discussed in detail.The development and design of catalysts with high efficiency were introduced from three aspects:the catalyst support,active component and atomic impurity.In addition,the coupling of DSHP and other oxidation reactions to realize one-pot in situ oxidation reactions was comprehensively emphasized,which showed essential guiding significance for the future development of H_(2)O_(2).展开更多
基金National Natural Science Foundation of China(T2188101)。
文摘Among the synthesis techniques for graphene,chemical vapor deposition(CVD)enables the direct growth of graphene films on insulating substrates.Its advantages include uniform coverage,high quality,scalability,and compatibility with industrial processes.Graphene is chemically inert and has a zero-bandgap which poses a problem for its use as a functional layer,and nitrogen doping has become an important way to overcome this.Post-plasma treatment has been explored for the synthesis of nitrogen-doped graphene,but the procedures are intricate and not suitable for large-scale production.We report the direct synthesis of nitrogen-doped graphene on a 4-inch sapphire wafer by ethanol-assisted CVD employing pyridine as the carbon feedstock,where the nitrogen comes from the pyridine and the hydroxyl group in ethanol improves the quality of the graphene produced.Additionally,the types of nitrogen dopant produced and their effects on III-nitride epitaxy were also investigated,resulting in the successful illumination of LED devices.This work presents an effective synthesis strategy for the preparation of nitrogen-doped graphene,and provides a foundation for designing graphene functional layers in optoelectronic devices.
基金Supported by the National Natural Science Foundation of China(20072005)Guangzhop Science and Technology Program.
文摘Dimethyl carbonate(DMC)has many excellent properties[1]and can be produced by many methods[2].The direct synthesis of DMC from CO_(2),CO_(2)+2CH_(3)OH==DMC+H_(2)O,has some advan-tages[3]as compared with other methods,but the conversion is very low because the reaction equilibrium is to the left and the reaction can only proceed under special conditions[4].
基金supported by the National Natural Science Foundation of China(91534127,U1463205)the Innovation Scientists and Technicians Troop Construction Projects of Henan Provincethe Chinese Education Ministry 111 Project(B08021)~~
文摘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.
基金Financial supports by the National Natural Science Foundation of China(21776210)Science and Technology Research Project of Henan Province(No.202102210048)。
文摘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).
基金financially supported by the National Key Research and Development Program of China(No.2016YFB0300500)the Youth Innovation Promotion Association CAS(No.2021294)+1 种基金the National Natural Science Foundation of China(No.51571047)Ningbo Major Special Projects of the Plan"Science and Technology Innovation 2025"(No.2018B10084)。
文摘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.
基金supported by the National Natural Science Foundation of China(21878143,21476106,21838004)Joint Re-search Fund for Overseas Chinese Scholars and Scholars in Hong Kong and Macao Young Scholars(21729601)+1 种基金the fund of State Key Laboratory of Materials-Oriented Chemical Engineering(ZK201702)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)~~
文摘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.
文摘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.
文摘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.
基金financial support from the National Natural Science Foundation of China(NSFC-21625604,91934302,and 22008211)Zhejiang Innovation Team(2017R5203)。
文摘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).
文摘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%.
基金supported by the Beijing Natural Science Foundation of China(2182040)the National Natural Science Foundation of China(51674026,U1802253)+1 种基金the Fundamental Research Funds for the Central Universities(FRF-TT-19-001)the China Scholarship Council(201906465004)。
文摘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.
文摘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.
基金support from Jiangxi Education Science FoundationNanchang University Science Foundation.
文摘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.
文摘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 .
文摘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.
文摘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.
基金Supported by the National Key Basic Research Program of China(2013CB733505,2013CB733501)the National Natural Science Foundation of China(91334202)+2 种基金the Natural Science Foundation of Jiangsu Province of China(BK2012421,BK20130062)the Research Fund for the Doctoral Program of Higher Education of China(20123221120015)the Project for Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)
文摘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.
基金supported by the National Key Research and Development Program of China(No.2022YFE0110300)the National Natural Science Foundation of China(No.52372215)+4 种基金the Special Fund for the“Dual Carbon”Science and Technology Innovation of Jiangsu province(Industrial Prospect and Key Technology Research program)(Nos.BE2022023,BE2022021)the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(No.21KJA430004)Gusu Innovation and Entrepreneurship Leading Talent Program(No.ZXL2022451)supported by Suzhou Key Laboratory of Functional Nano&Soft Materials,Collaborative Innovation Center of Suzhou Nano Science&Technologythe 111 Project.Y.L.thanks the Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX23_3241)for financial support.J.Y.X.thanks the support of Hui-Chun Chin and Tsung-Dao Lee Chinese Undergraduate Research Endowment(CURE).
文摘The direct synthesis of semi-conductive quantum dot(QD)inks coordinated by inorganic ions in polar phases presents potential advantages such as low cost and scalability,making it an ideal approach for realizing QDs-based optoelectronic applications.However,the weak repulsive forces between QDs coordinated by inorganic ions can easily lead to agglomeration,significantly limiting size control during the synthesis process.Distinct from the traditional high-temperature injection and low-temperature growth strategy used in the synthesis of QDs with long-chain organic ligands,we discover that low-temperature injection nucleation and high-temperature growth is an effective strategy to achieve controllable tuning of reactive monomers and ligand ions in the direct synthesis system of inorganic ion-liganded QD inks,which in turn realizes the scalable,low-cost,and direct synthesis of uniform and size-tunable short-wavelength infrared(SWIR)PbS QD inks.The yield of single synthesis can be more than 10 g.Compared with the traditional ligand exchange method,the yield is improved by nearly 3 times and the cost is reduced to 7 times.Finally,the solar cell devices fabricated using these PbS SWIR QD inks achieved a photovoltaic conversion efficiency of approaching 9%,confirming the excellent optoelectronic performance of the synthesized PbS QD materials.
基金supported by the National Natural Science Foundation of China(22101039,22471027,22311530679)the Science Fund for Creative Research Groups of the National Natural Science Foundation of China(22021005)the Fundamental Research Funds for the Central Universities(DUT24LK004).
文摘Metal-organic frameworks(MOFs)have garnered widespread attention due to their designability and diversity[1].Customization has always been a pursuit of chemists and materials scientists[2].Topology provides a means of abstracting the complex structures of MOFs by identifying and classifying the fundamental building units and connection patterns,simplifying the understanding of MOF structures[3].
基金This work is supported by the National Key R&D Program of China(2021YFB3801600)the National Natural Science Foundation of China(22078005).
文摘Hydrogen peroxide(H_(2)O_(2))is a green oxidant that has been widely used.The direct synthesis of hydrogen peroxide(DSHP)offers significant advantages in terms of high atomic economy and environmentally friendly effects.However,due to the inevitable side reactions and severe mass transfer limitations,it is still challenging to balance the selectivity and activity for the DSHP.Combining theoretical understanding with the controllable synthesis of nanocatalysts may significantly facilitate the design of“dream catalysts”for the DSHP.In this work,the main factors affecting the reaction performance of catalysts and the active sites of catalysts have been reviewed and discussed in detail.The development and design of catalysts with high efficiency were introduced from three aspects:the catalyst support,active component and atomic impurity.In addition,the coupling of DSHP and other oxidation reactions to realize one-pot in situ oxidation reactions was comprehensively emphasized,which showed essential guiding significance for the future development of H_(2)O_(2).
