粉煤灰基沸石分子筛的合成及应用进展

煤炭在燃烧利用过程中产生大量的粉煤灰。我国粉煤灰产量高居世界第1位,由于综合利用率只有70%,仍有大量粉煤灰露天堆存,造成严重的环境污染和资源浪费。消除粉煤灰的环境污染、提高其资源化利用率对我国循环经济的发展具有重要的现实意义。我国粉煤灰的利用由早期的粗放型规模化利用逐渐向精细型高值化利用转变。由于粉煤灰中富含硅铝元素,以粉煤灰为原料合成沸石分子筛是近年来粉煤灰高值化利用的研究热点。从4个方面对粉煤灰基沸石分子筛的合成及应用展开论述。首先,介绍了粉煤灰的形成、物化性质及其危害和治理利用现状。粉煤灰是一些矿物组成不同、形态不同的颗粒的机械混合物,其性质与原煤的成分、产地和燃烧方式有关。而粉煤灰的特性是决定其综合利用方式的关键。其次,论述了粉煤灰的3种主要活化方式,包括机械活化、水热活化和碱(盐)融活化。粉煤灰中的硅铝元素主要以非晶矿物玻璃体形式存在,其表面是致密的玻璃质外壳,粉煤灰合成沸石分子筛的关键问题是如何使硅和铝被充分活化,并得到有效利用。相比于机械研磨活化和碱(盐)熔融活化,水热活化有更高的活化效率和较低的能耗。第3部分论述了粉煤灰基沸石分子筛放入水热合成方法,重点介绍了直接水热合成法、碱融-水热合成法、微波/超声波-水热合成法、晶种法和转晶法。粉煤灰合成沸石分子筛一般均基于水热合成过程,多步水热处理可提高产物纯度,辅以超声、微波、碱熔融和添加晶种等方法可提高产率、晶化速率和结晶度。转晶法可极大拓展粉煤灰基沸石的骨架类型和酸性位,是更有利的粉煤灰基沸石分子筛的制备技术。最后,概述了粉煤灰基沸石分子筛的应用。粉煤灰基沸石分子筛的应用尚处于探索阶段,主要用于环境治理领域,包括工业废水中重金属离子的吸附脱除、大气污染物的吸附脱除以及温室气体CO_(2)吸附。

Metal-organic frameworks MOF-808-X as highly efficient catalysts for direct synthesis of dimethyl carbonate from CO_2 and methanol

A series of metal-organic frameworks MOF-808-X(6-connected)were synthesized by regulating the ZrOCl2·8H2O/1,3,5-benzenetricarboxylic acid(BTC)molar ratio(X)and tested for the direct synthesis of dimethyl carbonate(DMC)from CO2 and CH3OH with 1,1,1-trimethoxymethane(TMM)as a dehydrating agent.The effect of the ZrOCl2·8H2O/BTC molar ratio on the physicochemical properties and catalytic performance of MOF-808-X was investigated.Results showed that a proper ZrOCl2·8H2O/BTC molar ratio during MOF-808-X synthesis was fairly important to reduce the redundant BTC or zirconium clusters trapped in the micropores of MOF-808-X.MOF-808-4,with almost no redundant BTC or zirconium clusters trapped in the micropores,exhibited the largest surface area,micropore size,and the number of acidic-basic sites,and consequently showed the best activity among all MOF-808-X,with the highest DMC yield of 21.5% under the optimal reaction conditions.Moreover,benefiting from the larger micropore size,MOF-808-4 outperformed our previously reported UiO-66-24(12-connected),which had even more acidic-basic sites and larger surface area than MOF-808-4,mainly because the larger micropore size of MOF-808-4 provided higher accessibility for the reactant to the active sites located in the micropores.Furthermore,a possible reaction mechanism over MOF-808-4 was proposed based on the in situ FT-IR results.The effects of different reaction parameters on DMC formation and the reusability of MOF-808-X were also studied.

Application of atomic layer deposition in fabricating high-efficiency electrocatalysts

Electrocatalysis is a promising approach to clean energy conversion due to its high efficiency and low environmental pollution. Noble metal materials have been studied to show high activity toward electrocatalyltic reactions, although such applications remain restricted by the high cost and poor durability of the noble metals. By precisely adjusting the catalyst composition, size, and structure, electrocatalysts with excellent performance can be obtained. Atomic layer deposition(ALD) is a technique used to produce ultrathin films and ultrafine nanoparticles at the atomic level. It possesses unique advantages for the controllable design and synthesis of electrocatalysts. Furthermore, the homogenous composition and structure of the electrocatalysts prepared by ALD favor the exploration of structure-reactivity relationships and catalytic mechanisms. In this review, the mechanism, characteristics, and advantages of ALD in fabricating nanostructures are introduced first. Subsequently, the problems associated with existing electrocatalysts and a series of recently developed ALD strategies to enhance the activity and durability of electrocatalysts are presented. For example, the deposition of ultrafine Pt nanoparticles to increase the utilization and activity of Pt, fabrication of core–shell, overcoat, nanotrap, and other novel structures to protect the noble-metal nanoparticles and enhance the catalyst stability. In addition, ALD developments in synthesizing non-noble metallic electrocatalysts are summarized and discussed. Finally, based on the current studies, an outlook for the ALD application in the design and synthesis of electrocatalysts is presented.

Catalytic roles of the acid sites in different pore channels of H‐ZSM‐5 zeolite for methanol‐to‐olefins conversion

H‐ZSM‐5 zeolite is a typical catalyst for methanol‐to‐olefins(MTO)conversion.Although the performance of zeolite catalysts for MTO conversion is related to the actual location of acid sites in the zeolite framework,the catalytic roles of the acid sites in different pore channels of the H‐ZSM‐5 zeolite are not well understood.In this study,the MTO reaction network,involving the aromatic cycle,alkene cycle,and aromatization process,and also the diffusion behavior of methanol feedstock and olefin and aromatic products at different acid sites in the straight channel,sinusoidal channel,and intersection cavity of H‐ZSM‐5 zeolite was comparatively investigated using density functional theory calculations and molecular dynamic simulations.The results indicated that the aromatic cycle and aromatization process occurred preferentially at the acid sites in the intersection cavities with a much lower energy barrier than that at the acid sites in the straight and sinusoidal channels.In contrast,the formation of polymethylbenzenes was significantly suppressed at the acid sites in the sinusoidal and straight channels,whereas the alkene cycle can occur at all three types of acid sites with similar energy barriers and probabilities.Consequently,the catalytic performance of H‐ZSM‐5 zeolite for MTO conversion,including activity and product selectivity,can be regulated properly through the purposive alteration of the acid site distribution,viz.,the location of Al in the zeolite framework.This study helps to elucidate the relation between the catalytic performance of different acid sites in the H‐ZSM‐5 zeolite framework for MTO conversion,which should greatly benefit the design of efficient catalyst for methanol conversion.

Solid base catalysts derived from Ca-M-Al(M = Mg, La, Ce, Y) layered double hydroxides for dimethyl carbonate synthesis by transesterification of methanol with propylene carbonate

Composite solid base catalysts derived from Ca‐M‐Al(M=Mg,La,Ce,Y)layered double hydroxides(LDH)were synthesized,characterized and applied to the transesterification of methanol with propylene carbonate.X‐ray diffraction analyses of the catalysts show that all of the catalysts were in the form of composite oxides.Compared with the Ca‐Al LDH catalyst,the specific surface areas and pore volumes of the catalysts were increased with the introduction of Mg,La or Ce.The catalytic performance of these catalysts increases in the order of Ca‐Y‐Al<Ca‐Al<Ca‐Ce‐Al<Ca‐La‐Al<Ca‐Mg‐Al,which is consistent with the total surface basic amounts of these materials and the formation of especially strong basic sites following modification with Mg and La.The Ca‐Mg‐Al catalyst shows the highest(Ca+Mg):Al atomic ratio,indicating that it likely contains more unsaturated O2?ions,providing it with the highest concentration of very strong basic sites.The recyclability of these catalysts is improved following the addition of Mg,La,Ce or Y,with the Ca‐Mg‐Al maintaining a high level of activity after ten recycling trials.X‐ray diffraction analyses of fresh and used Ca‐Mg‐Al demonstrate that this catalyst is exceptionally stable,which could be of value in practical applications related to heterogeneous catalysis.

CO_2 hydrogenation to methanol over Cu/Zn/Al/Zr catalysts prepared by liquid reduction

Cu/Zn/Al/Zr catalysts containing Cu in three valence states(Cu2+,Cu+and Cu0)were prepared usinga liquid reduction method and subsequently calcined at different temperatures.The effects of thecalcination temperature on the catalyst structure,interactions among components,reducibility anddispersion of Cu species,surface properties and exposed Cu surface area were systematically investigated.These materials were also applied to the synthesis of methanol via the hydrogenation ofCO2.The results show that a large exposed Cu surface area promotes catalytic CO2conversion andthat there is a close correlation between the Cu+/Cu0ratio and the selectivity for methanol.A calcinationtemperature of573K was found to produce a Cu/Zn/Al/Zr catalyst exhibiting the maximumactivity during the synthesis of methanol.

Photoelectrocatalytic CO2 reduction based on metalloporphyrin-modified TiO2 photocathode

The conversion of CO2 and water to value-added chemicals under sunlight irradiation, especially by photoelectrocatalytic reduction process, is always a dream for human beings. A new artificial photosynthesis system composed of a metalloporphyrin-functionalized TiO2 photocathode and BiVO4 photoanode can efficiently transform CO2 and water to methanol, which is accompanied by oxygen release. This photoelectrocatalytic system smoothly produces methanol at a rate of 55.5 μM h^–1 cm^– 2, with 0.6 V being the membrane voltage in plants. The production of hydrogen can also be observed when the voltage is more than 0.75 V, due to photocatalysis. Our results evidently indicate that the molecules of metalloporphyrin attached onto the surface of anatase (TiO2) behave as chlorophyll, NADP, and Calvin cycle in plant cells.

N‐doped carbon modified Pt/CNTs synthesized by atomic layer deposition with enhanced activity and stability for methanol electrooxidation

A Pt/CNTs catalyst coated with N‐doped carbon（xNC‐Pt/CNTs） is synthesized by atomic layer dep‐osition（ALD） and applied in methanol electrooxidation reaction. Pt nanoparticles and polyimide（PI） are sequentially deposited on carbon nanotubes（CNTs） by ALD. After annealing at 600 °C in H2 atmosphere, the PI is carbonized to produce porous N‐doped carbon. Upon coating with a moder‐ately thick layer of N‐doped carbon, the optimized 50 NC‐Pt/CNTs show higher activity, better long‐term stability, and improved CO resistance towards methanol electrooxidation compared with Pt/CNTs and commercial Pt/C（20 wt%）. X‐ray photoelectron spectroscopy characterization result indicates that the Pt–CO bond is weakened after N‐doped carbon coating and CO adsorption on the Pt surface is weakened, leading to superior electrocatalytic performance.

Perpendicular intergrowth ZSM-5 plates with shortened 10-MR pores

ZSM-5 plates with a perpendicular intergrowth structure was synthesized by using a simple amine as the structure directing agent under hydrothermal conditions,in which the mother plate and the perpendicularly standing plates oriented along the(010)and(100)planes of MFI crystals,respectively.During the crystallization process,the mother plate was initially formed on the surface of the amorphous solid gel,while a set of parallel plates perpendicularly grew on its surface,via a homogeneous nucleation mechanism.The mother plate and the perpendicular plates had a similar thickness of 100-200 nm and were characterized by considerably shortened straight and zigzag 10 member ring pores,respectively.This unique intergrowth structure greatly facilitated the diffusion of the reactive molecules in HZSM-5 crystals during methanol conversion to hydrocarbons.

Cu_2O/SiC as efficient catalyst for Ullmann coupling of phenols with aryl halides

A Cu2O/SiC heterogeneous catalyst was prepared via a two‐step liquid‐phase method using diethyleneglycol as both the solvent and the reducing agent.The catalyst was characterized using X‐raydiffraction,X‐ray photoelectron spectroscopy,scanning electron microscopy(SEM),transmissionelectron microscopy(TEM),and H2temperature‐programmed reduction.All the results indicatethat Cu is present on the SiC support primarily as Cu2O.The SEM and TEM results show that cubicCu2O nanoparticles are uniformly dispersed on theβ‐SiC surface.The reaction conditions,namelythe temperature,reaction time,and amounts of base and catalyst used,for the Ullmann‐type C–Ocross‐coupling reaction were optimized.A model reaction was performed using iodobenzene(14.0mmol)and phenol(14.0mmol)with Cu2O/SiC(5wt%Cu)as the catalyst,Cs2CO3(1.0equiv.)as thebase,and tetrahydrofuran as the solvent at150°C for3h;a yield of97%was obtained and theturnover frequency(TOF)was1136h?1.The Cu2O/SiC catalyst has a broad substrate scope and canbe used in Ullmann‐type C–O cross‐coupling reactions of aryl halides and phenols bearing a varietyof different substituents.The catalyst also showed high activity in the Ullmann‐type C–Scross‐coupling of thiophenol with iodobenzene and substituted iodobenzenes;a TOF of1186h?1was achieved.The recyclability of the Cu2O/SiC catalyst in the O‐arylation of phenol with iodobenzenewas investigated under the optimum conditions.The yield decreased from97%to64%afterfive cycles.The main reason for the decrease in the catalyst activity is loss of the active component,i.e.,Cu2O.

In situ preparation of mesoporous Fe/TiO_2 catalyst using Pluronic F127-assisted sol-gel process for mid-temperature NH_3 selective catalytic reduction

An Fe/TiO2catalyst with uniform mesopores was synthesized using Pluronic F127as a structuredirecting agent.This catalyst was used for selective catalytic reduction of NO with NH3.The catalytic activity and resistance to H2O and SO2of Fe/TiO2prepared by a template method were better than those of catalysts synthesized using impregnation and coprecipitation.The samples were characterized using N2‐physisorption,transmission electron microscopy,ultraviolet‐visibl spectroscopy,X‐ray photoelectron spectroscopy,and in situ diffuse reflectance infrared Fouriertransform spectroscopy.The results showed that Pluronic F127acted as a structural and chemical promoter;it not only promoted the formation of a uniform mesoporous structure,leading to a higher surface area,but also improved dispersion of the active phase.In addition,the larger number of Lewis acidic sites,indicated by the presence of coordinated NH3species(1188cm-1)and the N–H stretching modes of coordinated NH3(3242and3388cm-1),were beneficial to mid‐temperature selective catalytic reduction reactions.

Photocatalytic-controlled olefin isomerization over WO_(3-x)using low-energy photons up to 625 nm

WO_(3-X)(W-l)was used to achieve controllable photoisomerization of linear olefins without substituents under 625 nm light irradiation.Thermodynamic and kinetic isomers were obtained by regulating the carbon chain length of the olefins.Terminal olefins were converted into isomerized products,and the internal olefin mixtures present in petroleum derivatives were transformed into valuable pure olefin products.Oxygen vacancies(OVs)in W-1 altered the electronic structure of W-1 to improve its light-harvesting ability,which accounted for the high activity of olefin isomerization under light irradiation up to 625 nm.Additionally,OVs on the W-1 surface generated unsaturated W^(5+)sites that coordinated with olefins for the efficient adsorption and activation of olefins.Mechanistic studies reveal that the in situ formation of surface Ti-complexes and ir-allylic W intermediates originating from the coordination of coordinated unsaturated W^(5+)sites and olefins ensure high photocatalytic activity and selectivity of W-1 for the photocatalytic isomerization of olefins via a radical mechanism.

Photocatalytic C–X borylation of aryl halides by hierarchical SiC nanowire-supported Pd nanoparticles

Hierarchical Si C nanowire-supported Pd nanoparticles showed high photocatalytic activity for the C–X(X = Br, I) borylation of aryl halides at 30 °C. The Si C/Pd Mott-Schottky contact enhances the rapid transfer of the photogenerated electrons from Si C to the Pd nanoparticles. As a result, the concentrated energetic electrons in the Pd nanoparticles can facilitate the cleavage of C–I or C–Br bonds, which normally requires high-temperature thermal processes. We show that the present Pd/Si C photocatalyst is capable of catalyzing the transformation of a large variety of aryl halides to their corresponding boronate esters under visible light irradiation, with excellent yields.