Cu-石墨炔/双金属钨酸盐S型异质结协同增强光催化析氢

采用有机法和水热法合成了Cu-石墨炔和CoNiWO_(4)并构建Cu-石墨炔/CoNiWO_(4)S型异质结。在保留催化剂强氧化还原能力的同时,通过内建电场和能带弯曲的协同作用促进了光生载流子的高效分离和转移。Cu-石墨炔的引入有效提高了复合催化剂的光吸收能力和导电性,抑制了光生载流子的复合。同时,Cu-石墨炔独特的二维平面网络结构提供了丰富的活性位点,从而促进了光催化反应的进行。密度泛函理论(DFT)计算表明,Cu的表面等离子体共振效应产生的热电子转移到石墨炔上,促进氢气的析出。本研究为Cu-石墨炔和镍钴基催化剂在光催化制氢领域提供了新的参考。

CeO_(2)-Cu_(2)O_(2)D/3D S型异质结界面促进有序电荷转移以实现高效光催化析氢

快速的本征载流子复合严重限制了CeO_(2)基催化材料的光催化活性。在这里,提出了一种异质结界面工程策略,合理地进行界面调节。构建了具有强电子相互作用的2D/3D S型异质结。合成了一种用于固定在2D CeO_(2)边缘的3D Cu_(2)O颗粒的复合光催化剂。密度泛函理论(DFT)第一性原理计算和实验结果表明,CeO_(2)和Cu_(2)O之间形成强耦合的S型异质结电子传输界面,实现了高效的载流子分离和传输。复合催化剂的光催化析氢活性在以三乙醇胺为牺牲剂的体系中得到大幅提高,是CeO_(2)的48倍。此外,CeO_(2)-Cu_(2)O光催化剂还具有高度稳定的光催化氢活性。这为在新型纳米复合结构中构建独特界面提供了一种通用策略。

ZnCr基催化剂煅烧温度对异丁醇合成性能的影响

研究了煅烧温度对ZnCr基催化剂合成异丁醇性能的影响。结果表明,随着煅烧温度的升高,催化剂的活性和产物分布都发生了较大的变化。催化剂在较低的温度下煅烧,液相产物中醇主要是甲醇和异丁醇;在较高的温度下煅烧,液相产物醇的分布符合A-S-F方程。用BET、XRD、H2-TPR、XPS等技术手段对催化剂织构参数、体相结构、还原性能、表面组成进行表征。结果表明,在300℃煅烧时,催化剂中的ZnO和Cr2O3未完全形成非计量尖晶石ZnxCr2/3(1-x)O;400℃煅烧时,催化剂中形成了最多量非计量尖晶石ZnxCr2/3(1-x)O;当煅烧温度高于400℃时,随着煅烧温度进一步升高,非计量尖晶石ZnxCr2/3(1-x)O逐步发生了分解,生成了更多量的ZnO和Cr2O3,导致催化剂的活性随之下降。进一步证明了非计量尖晶石ZnxCr2/3(1-x)O是该催化反应活性相。

不同改性组分对Cu-ZnO基催化剂低温甲醇合成性能的影响

通过共沉淀法制备了Al、Zr和Ce改性的Cu-ZnO基低温甲醇合成催化剂,采用氮气物理吸附、H2-TPR、CO2-TPD、N2O滴定、XRD和TEM等技术对其进行了表征,并考察了改性组分和煅烧温度对其在170℃下合成气制甲醇催化性能的影响。结果表明,经Zr改性的Cu-ZnO基催化剂,其低温甲醇合成性能较好;随着煅烧温度的降低,Cu在催化剂表面的分散度逐渐变大、颗粒逐渐变小,所得到的催化剂其活性也较高;其中,未经煅烧的Cu-ZnO/ZrO2催化剂的活性最佳,其甲醇时空产率为106.02 g/(kg·h),选择性达87.04%。

Catalytic Oxidation of Dimethyl Ether to Dimethoxymethane over Cs Modified H_3PW_(12)O_(40)/SiO_2 Catalysts

The attractive utilization route for one-step catalytic oxidation of dimethyl ether to dimethoxymethane was successfully carried out over the H3PW12O40（40%）/SiO2 catalyst, modified by Cs, K, Ni, and V. The Cs modification of H3PW12O40（40%）/SiO2 gave the most promising result of 20% dimethyl ether conversion and 34.8% dimethoxymethane selectivity. Dimethoxymethane could be synthe- sized via methoxy groups decomposed from dimethyl ether through the synergistic effect between the acid sites and the redox sites of Cs modified H3PW12O40（40%）/SiO2.

A facile solvent-free synthesis strategy for Co-imbedded zeolite-based Fischer-Tropsch catalysts for direct gasoline production

A series of Co-imbedded zeolite-based catalysts were synthesized following a facile solvent-free grinding route.The catalytic performance for direct syngas conversion to gasoline range hydrocarbons was compared with their counterpart Co-impregnated zeolite-based catalysts.Successful transformation of solid raw materials to targeted zeolite was confirmed by XRD,SEM,STEM,and N2 physisorption analysis.An in-depth study of acidic strength and acidic site distribution was conducted by NH3-TPD and Py-IR spectroscopy.Acidic strength showed a pivotal role in defining product range.Co@S1,with the weakest acidic strength of silicalite-1 among three types of zeolites,evaded over-cracking of product and exhibited the highest gasoline and isoparaffin selectivity(≈70%and 30.7%,respectively).Moreover,the solvent-free raw material grinding route for zeolite synthesis accompanies several advantages like the elimination of production of wastewater,high product yield within confined crystallization space,and elimination of safety concerns regarding high pressure due to the absence of the solvent.Facileness and easiness of the solvent-free synthesis route together with promising catalytic performance strongly support its application on the industrial scale.

Tuning the crystallite size of monoclinic ZrO_(2) to reveal critical roles of surface defects on m–ZrO_(2) catalyst for direct synthesis of isobutene from syngas

The effects of crystallite size on the physicochemical properties and surface defects of pure monoclinic ZrO_(2) catalysts for isobutene synthesis were studied.We prepared a series of monoclinic ZrO_(2) catalysts with different crystallite size by changing calcination temperature and evaluated their catalytic performance for isobutene synthesis from syngas.ZrO_(2) with small crystalline size showed higher CO conversion and isobutene selectivity,while samples with large crystalline size preferred to form dimethyl ether(DME)instead of hydrocarbons,much less to isobutene.Oxygen defects(ODefects)analyzed by X-ray photoelectron spectroscopy(XPS)provided evidence that more ODefectsoccupied on the surface of ZrO_(2) catalysts with smaller crystalline size.Electron paramagnetic resonance(EPR)and ultraviolet–visible diffuse reflectance(UV–vis DRS)confirmed the presence of high concentration of surface defects and Zr3+on mZrO_(2)-5.9 sample,respectively.In situ diffuse reflectance infrared Fourier transform spectroscopy(in situ DRIFTS)analysis indicated that the adsorption strength of formed formate species on catalyst reduced as the crystalline size decreased.These results suggested that surface defects were responsible for CO activation and further influenced the adsorption strength of surface species,and thus the products distribution changed.This study provides an in-depth insight for active sites regulation of ZrO_(2) catalyst in CO hydrogenation reaction.

Fischer–Tropsch synthesis on impregnated cobalt-based catalysts:New insights into the effect of impregnation solutions and pH value

The Co-based catalysts were prepared with different cobalt acetate solutions. Effects of pH value were studied deeply on Fischer–Tropsch synthesis (FTS) through a semi-batch reactor. Among all impregnation solutions (water, butanol, amyl alcohol, acetic acid, nitric acid and ammonium nitrate), the catalyst prepared by NH4NO3solution showed the highest catalytic activity due to its small particle size and high reduction degree. However, the catalyst with the smallest particle size derived from water as impregnation solution exhibited low activity as well as high methane selectivity since it was difficult to be reduced and inactive in FTS. According to FT-IR spectra results, the low intensity of absorbed CO on the catalyst prepared from water solution resulted in low FTS activity. Whereas, the high activity of catalysts prepared from NH4NO3solution could be explained by the high intensity of absorbed CO on the catalysts. The cobalt species on the catalysts prepared under lower pH conditions exhibited smaller particle size distribution as well as lower CO conversion than those prepared at higher pH value. © 2016 Science Press

Active Fischer-Tropsch synthesis Fe-Cu-K/SiO_2 catalysts prepared by autocombustion method without a reduction step

The purpose of this study was to prepare iron-based catalysts supported on silica by autocombustion method for directly using for Fischer-Tropsch synthesis（FTS） without a reduction step. The effect of different citric acid（CA）：iron nitrate（N） molar ratios and acid types on the FTS performance of catalysts were investigated. The CA：N molar ratios had an important influence on the formation of iron active phases and FTS activity. The iron carbide（FexC）, which is known to be one of the iron active phases, was demonstrated by the X-ray diffraction and X-ray photoelectron spectroscopy. Increasing the CA：N molar ratios up to 0.1 increased CO conversion of catalyst to 86.5%, which was then decreased markedly at higher CA：N molar ratios. An excess of CA resulted in carbon residues covering the catalyst surface and declined FTS activity. The optimal catalyst（CA：N molar ratio = 0.1） achieved the highest CO conversion when compared with other autocombustion catalysts as well as reference catalyst prepared by impregnation method, followed by a reduction step. The autocombustion method had the advantage to synthesize more efficient catalysts without a reduction step. More interestingly, iron-based FTS catalysts need induction duration at the initial stage of FTS reaction even after reduction, because metallic iron species need time to be transformed to FexC. But here, even if without reduction, FexC was formed directly by autocombustion and induction period was eliminated during FTS reaction.

Sputtered nano-cobalt on H-USY zeolite for selectively converting syngas to gasoline

Selectively converting CO and H2 to gasoline product （isoparaffin and olefin） in one step still remains a great challenge. We demonstrate effective H-USY zeolite supported nano-cobalt bifunctional catalysts for this catalytic reaction, which are prepared by the novel physical sputtering process. Particles of the sputtered cobalt exist in nano-level and are well-dispersed on acid USY zeolite. Easy activation of the loaded nano-cobalt is also achieved in a low-temperature hydrogen reduction atmosphere. In the tandem catalytic reaction, the sputtered bifunctional Co/USY catalyst exhibits a much higher CO conversion and higher isoparaffin selectiv- ity than the conventional impregnated one. Compared with H-Mor, H-Beta and other zeolites supported catalysts, H-USY zeolite supported cobalt catalyst shows the clearest promotional effect on the activity of FischerTropsch synthesis. The described synthesis herein provides a new pathway to solve the problem caused by the strong metal-support interaction （MSI） in heterogeneous catalysis.

A mini review on recent advances in thermocatalytic hydrogenation of carbon dioxide to value-added chemicals and fuels

The development of industrialization has led to the increased demands for carbon-based energy resources, meanwhile, excessive carbon dioxide (CO_(2)) emission caused by industrialization has aroused enormous environmental concerns. With the proposal of global carbon neutrality, much attention has been paid to the thermocatalytic hydrogenation of CO_(2) into value-added chemicals and fuels, which is widely considered as a promising way to alleviate carbon emission and energy shortage. CO_(2) hydrogenation to hydrocarbons mainly undergoes a CO_(2)-modified Fischer-Tropsch synthesis (CO_(2)-FTS) route or a methanol-mediated (MeOH) route. However, each route needs to be further optimized and possesses its own advantages and disadvantages. In the present review, the mechanisms and primary intermediates of these two routes are firstly summarized. Hereafter, the current understandings of the relationship among catalytic performance, physical-chemical properties of catalysts and reaction conditions for each route are overviewed according to different target products, including light olefins, gasoline, jet fuel, diesel and aromatics. Finally, we provide an outlook of dual-pathway catalysts on future direction of CO_(2) hydrogenation.

One-step conversion of syngas to light olefins over bifunctional metal-zeolite catalyst

Light olefins(C_(2)–C_(4))are fundamental building blocks for the manufacture of polymers,chemical intermediates,and solvents.In this work,we realized a composite catalyst,comprising MnxZry oxides and SAPO-34 zeolite,which can convert syngas(CO+H_(2))into light olefins.MnxZry oxide catalysts with different Mn/Zr molar ratios were facilely prepared using the coprecipitation method prior to physical mixing with SAPO-34 zeolite.The redox properties,surface morphology,electronic state,crystal structure,and chemical elemental composition of the catalysts were examined using H_(2)-TPR,SEM,XPS,XRD,and EDS techniques,respectively.Tandem reactions involved activation of CO and subsequent hydrogenation over the metal oxide catalyst,producing methanol and dimethyl ether as the main reaction intermediates,which then migrated onto SAPO-34 zeolite for light olefins synthesis.Effects of temperature,pressure and reactant gas flow rate on CO conversion and light olefins selectivity were investigated in detail.The Mn_(1)Zr_(2)/SAPO-34 catalyst(Mn/Zr ratio of 1:2)attained a CO conversion of 10.8%and light olefins selectivity of 60.7%,at an optimized temperature,pressure and GHSV of 380℃,3 MPa and 3000h^(−1) respectively.These findings open avenues to exploit other metal oxides with CO activation capabilities for a more efficient syngas conversion and product selectivity.

Recent Advances in Multifunctional Capsule Catalysts in Heterogeneous Catalysis

Capsule catalysts composed of pre-shaped core catalysts and layer zeolites have been widely used in the tandem reactions where multiple continuous reactions are combined into one process. They show excellent catalytic performance in heterogeneous catalysis, including the direct synthesis of middle isoparaflins or dimethyl ether from syngas, as compared to the conventional hybrid catalysts. The present review highlights the recent development in the design of capsule catalysts and their catalytic applications in heterogeneous catalysis. The capsule catalyst preparation methods are introduced in detail, such as hydrothermal synthe- sis method, dual-layer method, physically adhesive method and single crystal crystallization method. Purthermore, several new applications of capsule catalysts in heterogeneous cat- alytic processes are presented such as in the direct synthesis of liquefied petroleum gas from syngas, the direct synthesis of para-xylene from syngas and methane dehydroaromatization. In addition, the development in the design of multifunctional capsule catalysts is discussed, which makes the capsule catalyst not just a simple combination of two dill）rent catalysts, but has some special functions such as changing the surface hydrophobic or acid properties of the core catalysts. Finally, the future perspectives of the design and applications of capsule catalysts in heterogeneous catalysis are provided.

HYDROTHERMAL CRACKING OF RESIDUAL OILS

The hydrothermal cracking of heavy oils, such as Canadian oil sand bitumen and Arabian heavy vacuum residue, as well as their model compound were performed over sulfided Ni/Al 2O 3 and NiMo/Al 2O 3 catalysts under 663～703 K and 6.0～8.0 MPa of hydrogen pressure in a batch autoclave reactor. According to the reaction mechanism of hydrothermal cracking, a small amount of free redical initiators, such as di tert peroxide, sulfur, etc., was added into the feed to generate free redicals at lower temperature, and obviously showed promotional effect on the conversion of hydrocarbons. The reaction mechanisms of hydrothermal cracking as well as the enhancing effect of initiators were studied by a probe reaction with 1 phenyldodecane as a model compound. The hydrothermal cracking of hydrocarbon proceeded via free redical mechanism and hydrogenating quench. The initiators might easily generate free redicals under reaction temperature, these redicals might abstract H from hydrocarbon molecule and reasonably initiate the chain reactions, therefore, promote the conversion of hydrocarbon even at lower reaction temperature.

S-scheme heterojunction in photocatalytic hydrogen production

As an ideal secondary energy source,hydrogen has the title of clean energy and the product of its complete combustion is only water,which is not polluting to the environment.Photocatalytic hydrogen production technology is an environmentally friendly,safe,and low-cost strategy that requires only an inexhaustible amount of solar energy and water as feedstock.This paper provides a detailed and detailed review of S-scheme heterojunction photocatalysts for photocatalytic hydrogen production,mainly including TiO_(2)-based,Perovskite-based,CdS-based,Graphitic phase carbon nitride-based,COF-based graphdiyne-based,ZnO-based,and ZnIn_(2)S_(4)-based S-scheme heterojunction photocatalysts.The classification of S-scheme heterojunctions is summarized.What’s more,various characterizations for direct verification of the charge migration mechanism of S-scheme heterojunctions are outlined.Based on the present study,the future potential challenges and future research trends for S-scheme heterojunctions in photocatalytic hydrogen evolution technology are pointed out,which provides feasible strategies for the development and design of S-scheme heterojunction photocatalysts in the field of photocatalytic hydrogen evolution.

Recent advancements and perspectives of the CO_(2)hydrogenation reaction

Owing to excessive carbon dioxide(CO_(2))emissions,which cause severe environmental issues,the conversion and utilization of CO_(2)have received increasing attention.Owing to its high efficiency and potential for industrial applications,converting CO_(2)into high value-added chemicals via thermocatalytic hydrogenation is a highly effective route among electrocatalytic,photocatalytic,and thermocatalytic CO_(2)conversion.In the past two decades,our group has developed novel CO_(2)hydrogenation technologies to produce chemicals such as aliphatic hydrocarbons,methanol(MeOH),ethanol,and aromatics(especially para-xylene,PX).In this review,we summarize the strategy for CO_(2)hydrogenation conversion and the novel rational design of catalysts,including low-temperature MeOH synthesis and capsule catalysts for tandem catalysis.We also discuss the challenges and opportunities of CO_(2)hydrogenation,such as CO_(2)capture,H2 prices,and carbon taxes.We hope to inspire new ideas for CO_(2)hydrogenation to produce high value-added chemicals through the design of catalysts and the exploration of reaction paths.

Facilitating efficient photocatalytic hydrogen evolution via enhanced carrier migration at MOF-on-MOF S-scheme heterojunction interfaces through a graphdiyne(C_(n)H_(2n-2))electron transport layer

Interface engineering of photocatalysts is an effective way to enhance their photocatalytic activity.In this work,the MOF-on-MOF strategy was used to construct the ZIF-9(Co)/Cu_(3)BTC_(2) photocatalyst in situ.Moreover,graph-diyne,possessing an inherent capability to facilitate rapid electron transfer at the interface,has been introduced into the ZIF-9(Co)/Cu_(3)BTC_(2) interface to regulate the interfacial carrier migration.The photogenerated carrier transfer capability has been significantly enhanced by the interfacial synergy,while retaining the original active sites and high specific surface area.The exceptional efficiency performance of the composite catalyst under identical conditions could be attributed to the following two key factors:(i)The interfacial S-scheme hetero-junction in ZIF-9(Co)/Cu_(3)BTC_(2) provides the composite catalyst with strong reduction activity,facilitating the involvement of additional electrons in the reduction reaction through bended bands and an internal electric field.(ii)Carrier dynamics analysis shows that graphdiyne,as an electron transport layer,accelerates the charge migration rate at the S-scheme heterojunction interface through the electron relay effect.The incorporation of graphdiyne greatly improves the catalytic activity of MOFs and also demonstrates the great potential of graph-diyne in photocatalysis.This work provides a feasible idea for the interface engineering design of graphdiyne in photocatalysts.

掺杂Nb、B等元素对MoVTe催化剂一步催化氧化丙烯制丙烯酸的影响

采用共沉淀法制备MoVTe复合氧化物系列催化剂,研究其一步氧化丙烯制备丙烯酸的催化性能,并采用XRD、ICP、EDS、H2-TPR、NH3-TPD对催化剂的结构、表面进行表征.结果表明,加入适量的Nb显著提高MoVTe复合氧化物对丙烯酸的选择性,可从34.1%提高至83.5%;同时丙烯酸的收率从24.7%提高到48.8%.适量Nb存在可以稳定催化剂表面Te元素,从而提高了丙烯酸的选择性;B、Fe、Ce、W元素掺杂对催化剂催化性能产生不同的影响,B掺杂提高了催化剂的催化性能,加入酸性元素硼可增加MoVTeNb复合氧化物催化剂表面丙烯活化位点(Te4+=O·Te3+─O·)的数目,使得丙烯转化率和丙烯酸收率显著提高,分别高达89.8%和64.8%.