The Capture and Catalytic Conversion of CO_(2) by Dendritic Mesoporous Silica-Based Nanoparticles

Dendritic mesoporous silica nanoparticles own three-dimensional center-radial channels and hierarchical pores,which endows themselves with super-high specific surface area,extremely large pore volumes,especially accessible internal spaces,and so forth.Dissimilar guest species(such as organic groups or metal nanoparticles)could be readily decorated onto the interfaces of the channels and pores,realizing the functionalization of dendritic mesoporous silica nanoparticles for targeted applications.As adsorbents and catalysts,dendritic mesoporous silica nanoparticles-based materials have experienced nonignorable development in CO_(2)capture and catalytic conversion.This comprehensive review provides a critical survey on this pregnant subject,summarizing the designed construction of novel dendritic mesoporous silica nanoparticles-based materials,the involved chemical reactions(such as CO_(2)methanation,dry reforming of CH_(4)),the value-added chemicals from CO_(2)(such as cyclic carbonates,2-oxazolidinones,quinazoline-2,4(1H,3H)-diones),and so on.The adsorptive and catalytic performances have been compared with traditional silica mesoporous materials(such as SBA-15 or MCM-41),and the corresponding reaction mechanisms have been thoroughly revealed.It is sincerely expected that the in-depth discussion could give materials scientists certain inspiration to design brand-new dendritic mesoporous silica nanoparticles-based materials with superior capabilities towards CO_(2)capture,utilization,and storage.

Catalytic conversion of lignocellulosic biomass into chemicals and fuels

In the search of alternative resources to make commodity chemicals and transportation fuels for a low carbon future,lignocellulosic biomass with over 180-billion-ton annual production rate has been identified as a promising feedstock.This review focuses on the state-of-the-art catalytic transformation of lignocellulosic biomass into value-added chemicals and fuels.Following a brief introduction on the structure,major resources and pretreatment methods of lignocellulosic biomass,the catalytic conversion of three main components,i.e.,cellulose,hemicellulose and lignin,into various compounds are comprehensively discussed.Either in separate steps or in one-pot,cellulose and hemicellulose are hydrolyzed into sugars and upgraded into oxygen-containing chemicals such as 5-HMF,furfural,polyols,and organic acids,or even nitrogen-containing chemicals such as amino acids.On the other hand,lignin is first depolymerized into phenols,catechols,guaiacols,aldehydes and ketones,and then further transformed into hydrocarbon fuels,bioplastic precursors and bioactive compounds.The review then introduces the transformations of whole biomass via catalytic gasification,catalytic pyrolysis,as well as emerging strategies.Finally,opportunities,challenges and prospective of woody biomass valorization are highlighted.

Production of Benzene from Lignin through Current Enhanced Catalytic Conversion

The directional production of benzene is achieved by the current-enhanced catalytic conversion of lignin. The synergistic effect between catalyst and current promotes the depolymerization of lignin and the selective recombinant of the functional groups in the aromatic monomers. A high benzene yield of 175 gbenzene/kglignin was obtained with an excellent selectivity of 92.9 C-mol%. The process potentially provides a promising route for the production of basic petrochemical materials or high value-added chemicals using renewable biomass.

In situ catalytic conversion of biomass fast pyrolysis vapors on HZSM–5

In situ catalytic conversion of biomass fast pyrolysis vapors was carried out on HZSM-5 with varying Si/Al ratios(ranging from 20 to 300) at 450 °C. The effects of Si/Al ratios of HZSM-5 zeolites on the distribution of biomass fast pyrolysis products and carbon deposits on catalysts were investigated. It was quite remarkable that after in situ catalytic conversion the amount of light phenols and hydrocarbons increased significantly while that of heavy phenols decreased a lot. Besides, the yield of cyclopentenones with relatively low oxygen content generally increased. It also indicated that as the Si/Al ratios of HZSM-5 increased, the amount of hydrocarbons and light phenols was found to drop greatly. The amount of carbon deposits was found to be around 8.5% with the exception of HZSM-5 with the Si/Al ratio of 300,which is much lower. Moreover, the carbon deposits yield dropped gradually with increasing Si/Al ratios of HZSM-5.Calcination of spent catalysts at 600 °C helped to restore the catalytic activity to a large extent despite a relatively lower efficiency of deoxygenation. Results indicated that HZSM-5 with relatively high acidity displayed great catalytic performance.

Catalytic Conversion of Biomass-Derived Polyols into Para-xylene over SiO2-Modified Zeolites

This work proved that biomass-based polyols (sorbitol, xylitol, erythritol, glycerol and ethanediol) were able to be converted into high-value chemical (p-xylene) by catalytic cracking of polyols, alkylation of aromatics, and the isomerization of xylenes over the SiO2-modified zeolites. Compared to the conventional HZSM-5 zeolite, the SiO2-containing zeolites considerably increased the selectivity and yield of p-xylene due to the reduction of external surface acidity and the narrowing of pore entrance. The influences of the methanol additive, reaction temperature, and types of polyols on the selectivity and yield of p-xylene were investigated in detail. Catalytic cracking of polyols with methanol significantly enhanced the production of p-xylene by the alkylation of toluene with methanol. The highest p-xylene yield of 10.9 C-mol% with a p-xylene/xylenes ratio of 91.1% was obtained over the 15wt%SiO2/HZSM-5 catalyst. The reaction pathway for the formation of p-xylene was addressed according to the study of the key reactions and the characterization of catalysts.

Catalytic Conversion of Alcohol to Corresponding Alkyl Chlorides

1-chloro-octane, 1-chloro-dedocane and 1-chloro-hexadecane are synthesized from the corresponding alcohols. The reactions are catalyzed by N, N-dimethyl formamide and dodecyltrimethyl animonium chloride, not only the reaction time has been reduced, but also the yield improved from 10%～20%.

Crystalline porous materials for catalytic conversion of lignin-related substances

The conversion of the biomass into eco-friendly fuels and chemicals has been exten-sively recognized as the essential pathway to achieve the sustainable economy and carbon neutral society.Lignin,as a kind of promising biomass energy,has been certified to produce the high-valued chemicals and fuels.Numerous efforts have been made to develop various catalysts for lignin catalytic conversion.Both metal-organic frameworks(MOFs)and covalent organic frameworks(COFs)belong to very important heterogeneous porous catalysts due to their regular porous struc-tures,high specific surface area,and precisely tailored diversities.In the review,thefirst part focused on the catalytic conversion of lignin,lignin model compounds,and lignin derivatives using the pristine MOFs,functional MOF composites,and MOF-derived materials.The second part summarized the catalytic conversion of lignin model compounds using pristine COFs and functional COF composites.The review here mainly concentrated on the design of the materials,screening of catalytic conditions,and explorations of the corresponded mechanisms.Specifically,(1)we summarized the MOF-and COF-based materials for the effects on the catalytic trans-formation of lignin-related substances;(2)we emphasized the catalytic mechanism of C–C and C–O bonds cleavage together with the structure–activity relationships;(3)we in-depth realized the relationship between the chemical/electronic/structural properties of the MOF-and COF-based catalysts and their catalytic performance for lignin-related substances.Finally,the challenges and future perspectives were also discussed on the catalytic conversion of lignin-related substances by MOF-and COF-based catalysts.

Oxygen defects boost polysulfides immobilization and catalytic conversion:First-principles computational characterization and experimental design

Although some experiments have shown that point defects in a cathode host material may enhance its performance for lithium-sulfur battery(LSB),the enhancement mechanism needs to be well investigated for the design of desired sulfur host.Herein,the first principle density functional theory(DFT)is adopted to investigate a high-performance sulfur host material based on oxygen-defective TiO2(D-TiO2).The adsorption energy comparisons and Gibbs free energy analyses verify that D-TiO2 has relatively better performances than defect-free TiO2 in terms of anchoring effect and catalytic conversion of polysulfides.Meanwhile,D-TiO2 is capable of absorbing the most soluble and diffusive long-chain polysulfides.The newly designed D-TiO2 composited with three-dimensional graphene aerogel(D-TiO2@Gr)has been shown to be an excellent sulfur host,maintaining a specific discharge capacity of 1,049.3 mAhg^−1 after 100 cycles at 1C with a sulfur loading of 3.2 mgcm^−2.Even with the sulfur mass loading increasing to 13.7 mgcm^−2,an impressive stable cycling is obtained with an initial areal capacity of 14.6 mAhcm^−2,confirming the effective enhancement of electrochemical performance by the oxygen defects.The DFT calculations shed lights on the enhancement mechanism of the oxygen defects and provide some guidance for designing advanced sulfur host materials.

Products and production routes for the catalytic conversion of seed oil into fuel and chemicals: a comprehensive review

With the depletion of fossil resources, there is a need to find alternative resources of fuels and chemicals. The use of renewable feedstock such as those from seed oil processing is one of the best available resources that have come to the fore-front recently. This paper critically analyzes and highlights major factors in the biodiesel industry, such as seeds oil composition, production methods, properties of biodiesel, problems and potential solutions of using vegetable seed oil, the composition, quality and effective utilization of crude glycerol, the catalytic conversion of glycerol into possible fuels and chemicals.

Effects of Dispersed Mo-Fe Catalysts on Catalytic Hydrothermal Conversion of Residue

Replacement of precious single metal catalysts with cost-effective,highly-dispersed composite catalysts for catalytic hydrothermal conversion of residue holds tremendous promise for the residue upgrading technologies.Organic metals were added to the feed as the oil-soluble precursors,and were transformed into the catalytic active phases in this work.Physical properties and structures of the composite catalysts had been investigated by X-ray fluorescence spectroscopy,X-ray photoelectron spectroscopy,X-ray diffraction,scanning electron microscopy and transmission electron microscopy.The composite catalysts were found to be highly efficient in the catalytic hydrothermal conversion of both the model compound and the residue.Increased metal dispersion and synergistic effects of two metals played indispensable roles in such catalytic system.Results showed that under the test conditions specified in the article,the catalyst had the best catalytic performance when the mass ratio of molybdenum to iron was 1.5.

Special Issue on Catalytic Activation and Selective Conversion of Energy-Related Molecules

The activation and selective conversion of energy-related molecules is an important research area of energy chemistry.The depletion of petroleum has stimulated research activities into the utilization of non-petroleum carbon resources such as natural gas(including conventional and

Solar-driven photothermal catalytic CO_(2) conversion:a review

It is highly desirable to seek green and sustainable technologies,such as employing photo thermal effects to drive energy catalysis processes to address the high energy demand and associated environmental impacts induced by the current methods.The photothermocatalysis process is an emerging research area with great potential in efficiently converting solar energy through various catalytic reactions.However,achieving simultaneously high conversion efficiency,cyclability,and durability is still a daunting challenge.Thus,tremendous work is still needed to enhance solar photo thermal catalytic conversion and promote its large-scale applications.This review developed the principles of coupling solar photon and thermal fields underlying the photothermal effect,exploration of efficient nanocatalysts,development of optofluidic reactor model,and photo thermal synergistic-driven CO_(2) reduction mechanisms.The ultimate goal was to provide an effective approach that can effectively convert solar energy into photocarriers/hot-electrons and heat,and importantly,can couple them to regulate catalysis reaction pathways toward the production of value-added fuel and chemical energy.

Liquid metal in prohibiting polysulfides shuttling in metal sulfides anode for sodium-ion batteries

Metal sulfides are a class of promising anode materials for sodium-ion batteries(SIBs)owing to their high theoretical specific capacity.Nevertheless,the reactant products(polysulfides)could dissolve into electrolyte,shuttle across separator,and react with sodium anode,leading to severe capacity loss and safety concerns.Herein,for the first time,gallium(Ga)-based liquid metal(LM)alloy is incorporated with MoS_(2)nanosheets to work as an anode in SIBs.The electron-rich,ultrahigh electrical conductivity,and self-healing properties of LM endow the heterostructured MoS_(2)-LM with highly improved conductivity and electrode integrity.Moreover,LM is demonstrated to have excellent capability for the adsorption of polysulfides(e.g.,Na_(2)S,Na_(2)S_(6),and S_(8))and subsequent catalytic conversion of Na_(2)S.Consequently,the MoS_(2)-LM electrode exhibits superior ion diffusion kinetics and long cycling performance in SIBs and even in lithium/potassium-ion battery(LIB/PIB)systems,far better than those electrodes with conventional binders(polyvinylidene difluoride(PVDF)and sodium carboxymethyl cellulose(CMC)).This work provides a unique material design concept based on Ga-based liquid metal alloy for metal sulfide anodes in rechargeable battery systems and beyond.

In situ induced cation-vacancies in metal sulfides as dynamic electrocatalyst accelerating polysulfides conversion for Li-S battery

Cation vacancy engineering is considered to be one of the effective methods to solve the issues of shuttling and sluggish redox kinetics of Li PSs owing to the intrinsic tunability of electronic structure.However,cation vacancies are few studied in the Li-S realm due to their complex and rigid preparation methods.In this work,one-step pyrolysis is reported to in situ introduce Fe-vacancies into iron sulfide(Fe_(0.96)S)as a sulfur host.For this host structure,Fe_(0.96)S is first employed as an adsorbent and catalyst in Li-S system.During the carbonization process,a tight contact structure of Fe_(0.96)S crystal and carbon network(Fe_(0.96)S@C)is in situ constructed,and the carbon layer as a conductor provides smooth electrons transfer pathways for redox reactions.Meanwhile,due to the introduction of Fe-vacancies in Fe S crystal,the adsorption capability and catalytic effect for Li PSs have been substantially enhanced.Moreover,the presence of Fe_(0.96)S crystal favors the mobility of electron and diffusion of Li+,which is revealed by the experiments and theoretical calculations.Through synergy respective advantages effect of Fe_(0.96)S and carbon,the Fe_(0.96)S@C-S cathode delivers high-rate capability at 5.0 C and stable long-life performance.Even under a high sulfur loading of 3.5 mg/cm^(2),the durable cyclic stability is still exhibited with the capacity retention of 93%over 400 cycles at 1.0 C,and the coulombic efficiency is≥98%.Noting that this strategy greatly simplifies the synthetic process of currently known cation-vacancy materials and furnishes a universal mentality for designing both divinable and astonishing new cation-vacancy materials.

Flower-like ZnO modified with BiOI nanoparticles as adsorption/catalytic bifunctional hosts for lithium–sulfur batteries

Due to the high specific capacity and energy density, lithium–sulfur battery is regarded as a potential energy storage conversion system. However, the serious shuttle effect and the sluggish electrochemical reaction kinetics impede the practical use of lithium–sulfur battery. In the interests of breaking through the above knotty problems, herein we propose to use the polar flower-like Zn O modified by Bi OI nanoparticles as bifunctional host with catalytic and adsorption ability for polysulfides in lithium–sulfur battery.It can be found that this adsorption/catalytic host integrates the functions of adsorption and mutual catalytic conversion of polysulfides, in which the polar flower-like Zn O can effectively capture the polysulfides through strong polar-polar interaction, simultaneously the BiOI nanoparticles can accelerate the mutual conversion of polysulfides to Li2 S through reducing the activation energy and conversion energy barrier required for the electrochemical reaction. As a result, under a sulfur loading of 2.5 mg cm^(-2), the lithium–sulfur battery with Zn O/Bi OI/CNT/S as cathode reveals a considerable initial specific capacity of1267 mAh g^(-1) at a current density of 0.1 C. Even the current density increased to 1 C, the capacity can reach as 873.4 mAh g^(-1), together with a good capacity retention of 67.1% after 400 cycles. Therefore,after systematically study the positive effects of the flower-like ZnO modified by catalytic BiOI nanoparticles on the adsorption and catalytic conversion of polysulfides, this work provides a new idea for the development and application of high-performance lithium–sulfur batteries.

Nano storage-boxes constructed by the vertical growth of MoS_(2 )on graphene for high-performance Li-S batteries

In order to accelerate the reaction kinetics of lithium-sulfur batteries, the introduction of electro catalysis and proper structural control of the sulfur cathode is urgently needed. MoS_(2) nano sheets was selectively grown vertically (V-MoS_(2)) on the microwave-reduced graphene (rGO) sheets through chemical coupling to construct a self-supporting sulfur cathode with a nano storage-box structure (V-MoS_(2) as the wall and rGO as the bottom). RGO, which has a high conductivity of 37 S cm^(−1), greatly accelerates the transfer of electrons from the active sites on the edge of the layer to the solution. The introduction of carbon tubes can connect the abundant pores in the foam and act as a long-range conductive path. The 2D-orthogonal-2D structure maximally exposes the edge active sites of MoS_(2), and together with graphene form a nano reactor of sulfur, intermediate lithium polysulfides and discharge product Li_(2)S(2). The effective combination of the microstructure confinement of the nano storage-boxes and the efficient synchronous catalytic mechanism of V-MoS_(2) greatly improves the electrochemical performance of the lithium-sulfur batteries. As a result, the assembled lithium-sulfur battery displays a high initial discharge capacity of 1379 mAh g^(−1), good cycle stability (86% capacity retention after 500 cycles at 0.1C) and superior rate performance.

Monodisperse polar NiCo_(2)O_(4) nanoparticles decorated porous graphene aerogel for high-performance lithium sulfur battery

Lithium sulfur battery(LSB)is a promising energy storage system to meet the increasing energy demands for electric vehicles and smart grid,while its wide commercialization is severely inhibited by the"shuttle effect"of polysulfides,low utilization of sulfur cathode,and safety of lithium anode.To overcome these issues,herein,monodisperse polar NiCo_(2)O_(4)nanoparticles decorated porous graphene aerogel composite(NCO-GA)is proposed.The aerogel composite demonstrates high conductivity,hierarchical porous structure,high chemisorption capacity and excellent electrocatalytic ability,which effectively inhibits the"shuttle effect",promotes the ion/electron transport and increases the reaction kinetics.The NCO-GA/S cathode exhibits high discharge specific capacity(1214.1 mAh g^(-1)at 0.1 C),outstanding rate capability(435.7 mAh g^(-1)at 5 C)and remarkable cycle stability(decay of 0.031%/cycle over 1000 cycles).Quantitative analyses show that the physical adsorption provided by GA mainly contributes to the capacity of NCO-GA/S at low rate,while the chemical adsorption provided by polar NiCo_(2)O_(4)contributes mainly to the capacity of NCO-GA/S with the increase of current density and cycling.This work provides a new strategy for the design of GA-based composite with synergistic adsorption and electrocatalytic activity for the potential applications in LSB and related energy fields.

Enhancing electrochemical conversion of lithium polysulfide by 1T-rich MoSe_(2) nanosheets for high performance lithium-sulfur batteries

The sluggish conversion kinetics and shuttle effect of lithium polysulfides(LiPSs)severely hamper the commercialization of lithium-sulfur batteries.Numerous electrocatalysts have been used to address these issues,amongst which,transition metal dichalcogenides have shown excellent catalytic performance in the study of lithium-sulfur batteries.Note that dichalcogenides in different phases have different catalytic properties,and such catalytic materials in different phases have a prominent impact on the performance of lithium-sulfur batteries.Herein,1T-phase rich MoSe_(2)(T-MoSe_(2))nanosheets are synthesized and used to catalyze the conversion of LiPSs.Compared with the 2H-phase rich MoSe_(2)(H-MoSe_(2))nanosheets,the T-MoSe_(2) nanosheets significantly accelerate the liquid phase transformation of LiPSs and the nucleation process of Li2S.In-situ Raman and X-ray photoelectron spectroscopy(XPS)find that T-MoSe_(2) effectively captures LiPSs through the formation of Mo-S and Li-Se bonds,and simultaneously achieves fast catalytic conversion of LiPSs.The lithium-sulfur batteries with T-MoSe_(2) functionalized separators display a fantastic rate performance of 770.1 mAh/g at 3 C and wonderful cycling stability,with a capacity decay rate as low as 0.065%during 400 cycles at 1 C.This work offers a novel perspective for the rational design of selenide electrocatalysts in lithium-sulfur chemistry.

Nano-flower spherical SnS2 combined with a special lithium storage mechanism as a multifunctional separator for lithium-sulfur batteries contributes to ultra-high initial discharge specific capacity

The critical factors that limit the electrochemical performance of lithium-sulfur(Li-S)batteries are mainly the“shuttle effect”of polysulfides and the slow redox reaction between lithium polysulfides(LiPSs).Herein,a nano-sphere-type material selfassembled from tin disulfide nanosheets is designed and applied to the Li-S cell separator in this work.The SnS_(2)@PP modified separator not only acts as a dual restriction for LiPSs by chemisorption and physical barrier.At the same time,it improves the catalytic activity of the redox reaction between LiPSs.The SnS_(2)has extremely high electrochemical activity.There,a portion of the lithium ions can be inserted into SnS_(2)to form Li_(x)SnS_(2)and contribute to the capacity during the first discharge of the battery.In addition,Li_(x)SnS_(2)possesses a high degree of stability,and it does not undergo further de-alloying reactions even at the high potential of the Li-S cell.The benefit is that the steady-state Li_(x)SnS_(2)acts as a lithium-containing substance.It can form special Li^(+)channels on the surface of the separator,thus greatly improving the efficiency of Li+transport.The results showed that the SnS_(2)@PP-based cell exhibited extremely high initial discharge specific capacity(1477 m Ah g^(-1)at 0.1 C)and excellent rate performance(631 m Ah g^(-1)at 5 C).Even after 1000 cycles at 2 C,the cell exhibited a low decay rate of 0.06%per cycle on average.In addition,the superior electrochemical performance was obtained even with a high sulfur loading of 5.1 mg cm^(-2)and low electrolyte of E/S=8μL mg^(-1).

Li_(2)ZnTi_(3)O_(8)as the host–separator modifier with efficient polysulfides trapping and fast Li^(+)diffusion for lithium-sulfur batteries

The diffusion and loss of lithium polysulfides(LiPSs)in lithium-sulfur batteries(LSBs)reduce the sulfur utilization rate and the catalytic conversion efficiency of sulfur species,resulting in early battery failure.Li_(2)ZnTi_(3)O_(8)(LZTO),characterized by its stable spinel structure,exhibits high Li+conductivity and holds great potential as an effective adsorbent for LiPSs.This study proposes a collaborative design concept of LZTO host–separator modifier,which offers a complementary and matching approach in the cathode side,effectively addressing the challenges associated with dissolution and inadequate conversion of LiPSs.Density functional theory(DFT)calculation substantiates the pronounced chemical affinity of LZTO towards LiPSs.More importantly,the high efficiency ion transport channels are achieved in separator coating due to the presence of the LZTO particles.Furthermore,the catalytic efficacy of LZTO is validated through meticulous analysis of symmetric batteries and Tafel curves.Consequently,the LZTO host–separator modifier-based cell displays satisfactory rate capability(1449 and 1166 mAh·g^(−1)at 0.1 and 0.5 C)and an impressively capacity(606 mAh·g^(−1)after 500 cycles at 1 C).The coordinated strategy of host–separator modifier is supposed to have wide applications in LSBs.