Catalytic performance of hierarchical H-ZSM-5/MCM-41 for methanol dehydration to dimethyl ether

Micro-mesoporous composite molecular sieves H-ZSM-5/MCM-41 were prepared by the hydrothermal technique with alkali-treated H-ZSM-5zeolite as the source and characterized by scanning electron microscopy,transmission electron microscopy,energy dispersive spectroscopy,X-ray diffraction,N2 adsorption-desorption measurement and NH3 temperature-programmed desorption.The catalytic performances for the methanol dehydration to dimethyl ether over H-ZSM-5/MCM-41 were evaluated.Among these catalysts,H-ZSM-5/MCM-41 prepared with NaOH dosage (nNa/nSi) varying from 0.4 to 0.47 presented excellent catalytic activity with more than 80%methanol conversion and 100%dimethyl ether selectivity in a wide temperature range of 170—300℃,and H-ZSM-5/MCM-41 prepared with nNa/nSi=0.47 showed constant methanol conversion of about 88.7%,100% dimethyl ether selectivity and excellent lifetime at 220℃.The excellent catalytic performances were due to the highly active and uniform acidic sites and the hierarchical porosity in the micro-mesoporous composite molecular sieves.The catalytic mechanism of H-ZSM-5/MCM-41 for the methanol dehydration to dimethyl ether process was also discussed.

3D printing of hydroxyapatite/tricalcium phosphate scaffold with hierarchical porous structure for bone regeneration

Three-dimensional(3D)-printed scaffolds have attracted considerable attention in recent years as they provide a suitable environment for bone cell tissue regeneration and can be customized in shape.Among many other challenges,the material composition and geometric structure have major impacts on the performance of scaffolds.Hydroxyapatite and tricalcium phosphate(HA/TCP),as the major constituents of natural bone and teeth,possess attractive biological properties and are widely used in bone scaffold fabrication.Many fabrication methods have been investigated in attempts to achieve HA/TCP scaffolds with microporous structure enabling cell growth and nutrient transport.However,current 3D printing methods can only achieve the fabrication of HA/TCP scaffolds with certain range of microporous structure.To overcome this challenge,we developed a slurry-based microscale mask image projection stereolithography,allowing us to form a HA/TCP-based photocurable suspension with complex geometry including biomimetic features and hierarchical porosity.Here,the curing performance and physical properties of the HA/TCP suspension were investigated,and a circular movement process for the fabrication of highly viscous HA/TCP suspension was developed.Based on these investigations,the scaffold composition was optimized.We determined that a 30 wt%HA/TCP scaffold with biomimetic hierarchical structure exhibited superior mechanical properties and porosity.Cell proliferation was investigated in vitro,and the surgery was conducted in a nude mouse in vivo model of long bone with cranial neural crest cells and bone marrow mesenchymal stem cells.The results showed our 3D-printed HA/TCP scaffold with biomimetic hierarchical structure is biocompatible and has sufficient mechanical strength for surgery.

Hierarchically Structured Monolithic ZSM-5 through Macroporous Silica Gel Zeolitization

The hierarchically structured ZSM-5 monolith was prepared through transforming the skeletons of the macroporous silica gel into ZSM-5 by the steam-assisted conversion method. The morphology and monolithic shapes of macroporous silica gel were well preserved. The hierarchically structured ZSM-5 monolith exhibited the hierarchical porosity, with mesopores and macropores existing inside the macroporous silica gel, and micropores formed by the ZSM-5. The products have been characterized properly by using the XRD, SEM and N2 adsorption–desorption methods.

Fabrication of Hierarchically Porous FAU/α-Al_(2)O_(3) Monoliths via Gel Pre-aging Routes Using Seed Gel as Directing Agent

Hierarchically porous FAU monoliths were synthesized via the gel pre-aging route using seed gel as directing agent andα-Al2O3 as monolithic carrier.The as-synthesized samples were characterized by means of the Fourier transform infrared spectroscopy(FT-IR),X-ray powder diffraction(XRD),scanning electron microscopy(SEM),and N2 adsorption techniques.The effects of seed gel,gel pre-treatment,and gel pre-aging step were determined,while the possible mechanism for formation of alumina composites via different synthesis processes were discussed.The results showed that the crystal size,the shape,and the loading of the supported FAU could be readily tuned by varying the composition of the crystallization gel without notably changing the structure ofα-Al2O3.The proposed seed gel pre-treating and gel pre-aging route are simple,reproducible,and practically easy to integrate triple porous structures into large-dimension monoliths,which are proved to be very effective in depositing pure FAU crystals on theα-Al2O3 skeleton surface and strengthening the interfacial interaction between them.Moreover,it may provide inspiration to the synthesis of other hierarchical zeolites.

A Radiative-Cooling Hierarchical Aligned Porous Poly(vinylidene fluoride)Film by Freeze-Thaw-Promoted Nonsolvent-Induced Phase Separation

Passive daytime radiative cooling(PDRC)is an innovative and sustainable cooling technology that holds immense potential for addressing the energy crisis.Despite the numerous reports on radiative coolers,the design of a straightforward,efficient,and readily producible system remains a challenge.Herein,we present the development of a hierarchical aligned porous poly(vinylidene fluoride)(HAP-PVDF)film through a freeze-thaw-promoted nonsolvent-induced phase separation strategy.This film features oriented microporous arrays in conjunction with random nanopores,enabling efficient radiative cooling performance under direct sunlight conditions.The incorporation of both micro-and nano-pores in the HAP-PVDF film results in a remarkable solar reflectance of 97%and a sufficiently high infrared thermal emissivity of 96%,facilitating sub-environmental cooling at 18.3℃ on sunny days and 13.1℃ on cloudy days.Additionally,the HAP-PVDF film also exhibits exceptional flexibility and hydrophobicity.Theoretical calculations further confirm a radiative cooling power of 94.8 W·m^(-2)under a solar intensity of 1000W·m^(-2),demonstrating a performance comparable to the majority of reported radiative coolers.

Dual-template strategy synthesis of hierarchically porous electrocatalysts for oxygen reduction reaction

Metal organic frameworks derived M-N-C catalysts have been discovered as promising alternatives to Pt-based catalysts in oxygen reduction reaction(ORR).However,the dominated micropores in their porous structures strongly restrain the mass transfer and lead to insufficient utilization of active sites.Here,we proposed a dualtemplate strategy to improve the catalytic performance of ZIF-8 derived M-N-C catalysts.Both the silica and sodium chloride templates created mesopores,which may intensified the mass transfer.Moreover,the molten sodium chloride connected the individual ZIF-8 crystals form highly graphitized carbon structure which had better stability and conductivity.The as-synthesized(FeCo)HPNC@NaCl catalyst exhibited similar ORR activity to commercial Pt/C under acidic conditions with half-wave potential of 0.808 V.The catalyst expressed high stability with 12 mV decrease of half-wave potential after 5000 cycles and 80%remained activity after 100000 s operation.Moreover,we tested the catalyst in fuel cell for practical application,achieving a high peak power density of 427 mW cm^(-2).

Hydrothermal conversion of lignocellulosic biomass into high-value energy storage materials

Preparation of hierarchically porous, heteroatom-rich nanostructured carbons through green and scalable routes plays a key role for practical energy storage applications. In this work, naturally abundant lignocellulosic agricultural waste with high initial oxygen content, hazelnut shells, were hydrothermally carbonized and converted into nanostructured ‘hydrochar’. Environmentally benign ceramic/magnesium oxide（Mg O） templating was used to introduce porosity into the hydrochar. Electrochemical performance of the resulting material（HM700） was investigated in aqueous solutions of 1 M H;SO;, 6 M KOH and1 M Na;SO;, using a three-electrode cell. HM700 achieved a high specific capacitance of 323.2 F/g in 1 M H;SO;（at 1 A/g,-0.3 to 0.9 V vs. Ag/Ag Cl） due to the contributions of oxygen heteroatoms（13.5 wt%）to the total capacitance by pseudo-capacitive effect. Moreover, a maximum energy density of 11.1 Wh/kg and a maximum power density of 3686.2 W/kg were attained for the symmetric supercapacitor employing HM700 as electrode material（1 M Na;SO;, E = 2 V）, making the device promising for green supercapacitor applications.

Influence of the post-treatment of HZSM-5 zeolite on catalytic performance for alkylation of benzene with methanol

The porous material HZSM-5 zeolite with micro-mesopore hierarchical porosity was prepared by post-treatment （combined alkali treatment and acid leaching） of parent zeolite and its catalytic performance for benzene alkylation with methanol was investigated. The effect of post-treatment on the textural properties was characterized by various techniques （including ICP-AES, XRD, nitrogen sorption isotherms, SEM, NH3-TPD, Py-IR and TG）. The results indicated that the post-treatment could modify the structural and acidic properties of HZSM-5 zeolite. In this procedure, not only additional mesopores were created by selective extraction of silicon but also the acidity was tuned. Consequently, the modified HZSM-5 zeolite showed larger external surface area with less acid sites as compared to the parent zeolite. It was found out that the modified zeolite exhibited a higher benzene conversion and xylene selectivity for alkylation of benzene with methanol as well as excellent life span of the catalyst than conventional ones. This can be explained by the facts that the presence of additional mesopores improved the diffusion property in the reactions. Furthermore, the modified zeolite showed an appropriate Bronsted acidity for effective suppression of the side reaction of methanol to olefins, thus reduced the accumulation of coke on the HZSM-5 zeolite, which was favorable for the catalyst stability. In comparison with the parent HZSM-5 zeolite, the modified zeolite by alkali treatment and acid leaching showed better performance for the benzene alkylation with methanol.

A Lightweight, Adhesive, Dual-Functionalized Over-Coating Interphase Toward Ultra-Stable High-Current Density Lithium Metal Anodes

Coherent manipulation of the lithium plating pattern is at the heart of the safe operation of metallic anodes in the battery technologies. In this article,a lightweight (~0.3 mg cm^(-2)), dual-functionalized carbon spheres are anchored onto the Cu foil as the interfacial protective layer via the chelation process of the catechol groups in the polydopamine precursor and the copper foil. The dual-functionalized carbon spheres exhibit the intriguing complementary features:Lithiophilic nitrogen dopants favor the Li+ion absorption and mitigate the nucleation barrier, while the micro/mesopore reservoir spatially homogenizes the ion flux distribution, confining the metallic propagation without dendrite-like protrusions. The metallic anode exhibits an ultra-stable plating/stripping process for 1 400 hr with the average Coulombic efficiency of ~99%. A full-cell prototype is constructed by pairing the N-doped carbon spheres on the bare Cu (NCS-Cu) electrode with the high-mass-loading LiVPO4F (12.5 mg cm^(-2)) cathode that can deliver a high energy density of 421.2 Wh kg^(-1) with the highest power density of 2106 W kg^(-1) to promise the anode use for high-power/energy-dense metallic batteries.

Rationally exfoliating chitin into 2D hierarchical porous carbon nanosheets for high-rate energy storage

Two-dimensional(2D)carbon nanomaterials with hierarchical porous structure and heteroatoms doping are highly desirable in the fields of energy storage because of their rich active surface and open ion diffusion channels.However,the scalable preparation of carbon materials simultaneously possessing ultrathin 2D feature and hierarchical pores remains a considerable challenge.Herein,a facile one-step method to massively fabricate 2D porous chitin nanosheets(coded as PCNs)via a phytic acid assisted top-down exfoliation of bulk chitin under hydrothermal treatment was presented.Subsequently,2D carbon nanosheets with extra-thin thickness(3.6 nm),well-defined hierarchical porosity,high specific surface area(855 m2·g^-1),as well as abundant self-doped heteroatoms(N,O,P)were fabricated by carbonizing the PCNs,and was named as HPCNs.The as-obtained HPCNs demonstrated remarkable electrochemical performance as electrode material for supercapacitors.The symmetric supercapacitors(SSCs)based on HPCNs exhibited a high specific capacitance of 79 F·g^-1(316 F·g^-1 for single electrode)in 6 M KOH aqueous electrolyte solution,as well as a remarkable energy density of 23.8 W·h·kg^-1 by using 1 M Li2SO4 as electrolyte.It is also demonstrated that HPCNs/PCNs hybrid dispersions can be used as inks to fabricate conductive films and energy devices with high strength and superior flexibility.This work paves a new avenue for the economical and large-scale synthesis of 2D hierarchically porous carbon materials for energy storage related applications.

Ni(OH)_2 nanoflakes supported on 3D hierarchically nanoporous gold/Ni foam as superior electrodes for supercapacitors

The increasing demand for portable electronic devices and hybrid electric vehicles stimulates the develop- ment of supercapacitors as an advanced energy storage system. Here, we demonstrate a binder-free nickel hydroxide@nano- porous gold/Ni foam （Ni（OH）2@NPG/Ni foam） electrode for high-performance supercapacitors, which is prepared by a facile three-step fabrication route including electrodeposition of Au-Sn alloy on Ni foam, chemical dealloying of Sn and electrodepostion of Ni（OH）2 on NPG/Ni foam. Such Ni（OH）2@NPG/Ni foam electrode is composed of a thin layer of conformable Ni（OH）2 nanoflakes supported on three-di- mensional （3D） hierarchically porous NPG/Ni foam substrate. The resulting Ni（OH）2@NPG/Ni foam electrode can offer highways for both electron transfer and ion transport and lead to an excellent electrochemical performance with an ultrahigh specific capacitance of 3,380 F g-1 at a current density of 2 A g-1. Even when the current density was increased to 50 A g-1, it still retained a high capacitance of 1,927 F g-1. The promising performance of the Ni（OH）2@NPG/Ni foam elec- trode is mainly ascribed to the 3D hierarchical porosity and the highly conductive network on the NPG/Ni foam composite current collector, as well as the conformal electrodeposition of Ni（OH）2 active material on the NPG/Ni foam, which induces the formation of interconnected porosity both on the top surface and on the inner surface of the electrode. This in- spiring electrochemical performance would make the as-de- signed electrode material become one of the most promising candidates for future electrochemical energy storage systems.

N-doped nanocarbon embedded in hierarchically porous metal-organic frameworks for highly efficient CO_(2) fixation

The rational integration of multi-functional components with metal–organic frameworks(MOFs) to form MOF-based catalysts can often afford enhanced catalytic activity for specific reactions. Herein, we propose a novel strategy for the synthesis of hierarchically porous MOFs(e.g., MIL-101)-encapsulated N-doped nanocarbon(CN@MIL) by controlled pyrolysis of ionic liquids@MIL-101 precursors(ILs@MIL). The obtained CN@MIL composites not only possess abundant enlarged mesopores,but also show multi-active sites without the sacrifice of their structure stability. The CN@MIL can efficiently facilitate the mass transfer of substrates, exhibiting excellent catalytic performance in the synthesis of cyclic carbonates from epoxides and CO_(2) under mild and co-catalyst-free conditions(i.e., 90 ℃ and ambient pressure of CO_(2)). Furthermore, the multi-active Lewis acid sites and nucleophilic sites(Br ions) as well as the strong affinity of catalysts toward CO_(2)also contribute to the excellent catalytic activity of the CN@MIL. This study might open a new avenue for the rational design of MOF-based composites by employing ILs@MOF as precursors for advanced heterogeneous catalysis.

Hierarchically porous carbon derived from natural Porphyra for excellent electromagnetic wave absorption

A highly efficient absorber with features including lightweight, broad bandwidth, and tunable electromagnetic property still remains challenging for practical applications. Herein, the Porphyra-derived porous carbon(PPC) was fabricated via facile procedures of low-temperature pre-carbonization combined with KOH chemical activation. The composition, microstructure, and electromagnetic wave absorption properties of the samples were elucidated based on X-ray diffraction(XRD), Raman, X-ray photoelectron spectroscopy(XPS), scanning electron microscopy(SEM), transmission electron microscopy(TEM),Brunauer-Emmer-Teller(BET), and vector network analyzer(VNA). The porosity of PPC can be readily regulated by adjusting activation temperature. The PPC obtained at 750 ℃ was composed of a threedimensional hierarchically porous carbon network. The C and N elements of natural Porphyra were introduced into the carbon skeleton during the carbonization process. The large specific surface, dopants, and three-dimensional hierarchically porous carbon network can effectively improve the impedance matching and dielectric dissipation, leading to an excellent electromagnetic wave absorption performance. Especially, the optimal reflection loss(RL) value reached –57.75 d B at 9.68 GHz with a broad bandwidth(RL< –10 d B) value of 7.60 GHz at 3.5 mm. Overall, the results indicate that the PPC can provide a new way to achieve lightweight, effective, and sustainable absorbers.

Template-Free Synthesis of Ordered Mesoporous NiO/Poly (Sodium-4-Styrene Sulfonate) Functionalized Carbon Nanotubes Composite for Electrochemical Capacitors

We report the first example of a practical and efficient template-free strategy for synthesizing ordered mesoporous NiO/poly(sodium-4-styrene sulfonate)(PSS)functionalized carbon nanotubes(FCNTs)composites by calcining a Ni(OH)_(2)/FCNTs precursor prepared by refl uxing an alkaline solution of Ni(NH_(3))x^(2)+and FCNTs at 97 oC for 1 h.The morphology and structure were characterized by X-ray diffraction,scanning electron microscopy,and transmission electron microscopy.Thermal decomposition of the precursor results in the formation of ordered mesoporous NiO/FCNTs composite(ca.48 wt%NiO)with large specifi c surface area.Due to its enhanced electronic conductivity and hierarchical(meso-and macro-)porosity,composite simultaneously meets the three requirements for energy storage in electrochemical capacitors at high rate,namely,good electron conductivity,highly accessibleelectrochemical surface areas owing to the existence of mesopores,and efficient mass transport from the macropores.Electrochemical data demonstrated that the ordered mesoporous NiO/FCNTs composite is capable of delivering a specifi c capacitance(SC)of 526 F/g at 1 A/g and a SC of 439 F/g even at 6 A/g,and show a degradation of only ca.6%in SC after 2000 continuous charge/discharge cycles.