Ethanol steam reforming over Ni/ZSM-5 nanosheet for hydrogen production

Compared to reforming reactions using hydrocarbons,ethanol steam reforming(ESR)is a sustainable alternative for hydrogen(H_(2))production since ethanol can be produced sustainably using biomass.This work explores the catalyst design strategies for preparing the Ni supported on ZSM-5 zeolite catalysts to promote ESR.Specifically,two-dimensional ZSM-5 nanosheet and conventional ZSM-5 crystal were used as the catalyst carriers and two synthesis strategies,i.e.,in situ encapsulation and wet impregnation method,were employed to prepare the catalysts.Based on the comparative characterization of the catalysts and comparative catalytic assessments,it was found that the combination of the in situ encapsulation synthesis and the ZSM-5 nanosheet carrier was the effective strategy to develop catalysts for promoting H_(2) production via ESR due to the improved mass transfer(through the 2-D structure of ZSM-5 nanosheet)and formation of confined small Ni nanoparticles(resulted via the in situ encapsulation synthesis).In addition,the resulting ZSM-5 nanosheet supported Ni catalyst also showed high Ni dispersion and high accessibility to Ni sites by the reactants,being able to improve the activity and stability of catalysts and suppress metal sintering and coking during ESR at high reaction temperatures.Thus,the Ni supported on ZSM-5 nanosheet catalyst prepared by encapsulation showed the stable performance with~88% ethanol conversion and~65% H_(2) yield achieved during a 48-h longevity test at 550-C.

Renewable hydrogen production from steam reforming of glycerol(SRG)over ceria-modified Y-alumina supported Ni catalyst

Excess crude glycerol derived as a by-product from biodiesel industry prompts the need to valorise glycerol to value-added chemicals.In this context,catalytic steam reforming of glycerol(SRG) was proposed as a promising and sustainable alternative for producing renewable hydrogen(H2).Herein,the development of nickel(Ni) supported on ceria-modified mesoporous γ-alumina(γ-Al2 O3) catalysts and their applications in catalytic SRG(at550-750℃ atmospheric pressure and weight hourly space velocity,WHSV,of 44,122 ml·g^-1·h^-1(STP)) is presented.Properties of the developed catalysts were characterised using many technique s.The findings show that ceria modification improved Ni dispersion on γ-Al2 O3 catalyst support with highly active small Ni particles,which led to a remarkable catalytic performance with the total glycerol conversion(ca.99%),glycerol conversion into gaseous products(ca.77%) and H2 yield(ca.62%).The formation rate for H2 production(14.4 ×10^(-5)mol·s^-1·g^-1, TOF(H2)=3412 s^-1) was significantly improved with the Ni@12 Ce-Al2 O3 catalyst,representing nearly a 2-fold increase compared with that of the conventional Ni@AI2 O3 catalyst.In addition,the developed catalyst also exhibited comparatively high stability(for 12 h) and coke resistance ability.

Structured hierarchical Mn–Co mixed oxides supported on silicalite-1 foam catalyst for catalytic combustion

Silicalite-1(S1)foam was functionalized by supporting manganese-cobalt(Mn-Co)mixed oxides to develop the structured hierarchical catalyst(Mn-Co@SlF)for catalytic combustion for the first time.The self-supporting S1 foam with hierarchical porosity was prepared via hydrothermal synthesis with polyurethane(PU)foam as the template.Subsequently,Mn-Co oxide nano sheets were uniformly grown on the surface of S1 foams under hydrothermal conditions to prepare the structured hierarchical catalyst with specific surface area of 354 m^2·g^-1,micropore volume of 0.141 cm^3·g^-1 and total pore volume of 0.217 cm3·g^-1,as well as a good capacity to adsorb toluene(1.7 mmol·g^-1 at p/p0=0.99).Comparative catalytic combustion of toluene of over developed structured catalyst Mn-Co@SlF was performed against the control catalysts of bulk Mn-Co@S1(i.e.,the crushed Mn-Co@SlF)and unsupported Mn-Co oxides(i.e.,Mn-Co).Mn-Co@SlF exhibited comparatively the best catalytic performance,that is,complete and stable toluene conversion at 2480 C over 65 h due to the synergy between Mn-Co oxides and S1 foam,which provided a large number of oxygen vacancies,high redox capacity.In addition,the hierarchical porous structure also improved the accessibility of active sites and facilitated the global mass transfer across the catalyst bed,being beneficial to the catalysis and catalyst longevity.

Systematic study of H2 production from catalytic photoreforming of cellulose over Pt catalysts supported on TiO2

Hydrogen(H2)production from photocatalytic reforming of cellulose is a promising way for sustainable H2 to be generated.Herein,we report a systematic study of the photocatalytic reforming of cellulose over Pt/m-TiO2(i.e.mixed TiO2,80%of anatase and 20%of rutile)catalysts in water.The optimum operation condition was established by studying the effect of Pt loading,catalyst concentration,cellulose concentration and reaction temperature on the gas production rate of H2(r(H2))and CO2(r(CO2)),suggesting an optimum operation condition at 40°C with 1.0 g·L^-1of cellulose and 0.75 g·L^-1of 0.16-Pt/m-TiO2 catalyst(with 0.16 wt%Pt loadting)to achieve a relatively sound photocatalytic performance with rH2=9.95μmol·h^-1.It is also shown that although the photoreforming of cellulose was operated at a relatively mild condition(i.e.with an UV-A lamp irradiation at40°C in the aqueous system),a low loading of Pt at^0.16 wt%on m-TiO2 could promote the H2 production effectively.Additionally,by comparing the reaction order expressed from both r(H2)(a1)and r(CO2)(a2)with respect to cellulose and water,the possible mechanism of H2 production was proposed.

Additive manufacturing of sodalite monolith for continuous heavy metal removal from water sources

Herein,we present a simple strategy for preparing monolithic sodalite adsorbents via sequential additive manufacturing and post-treatments.In detail,the method includes(i)3D printing of cylindrical monoliths using clay as the base material;(ii)thermal activation of the 3D-printed clay monoliths by calcination(to produce reactive alumina and silica species and enable mechanical stabilization);(iii)conversion of the activated clay monoliths to hierarchical porous sodalite monoliths via hydrothermal alkaline treatment.Parametric studies on the effect of calcination temperature,alkaline concentration and hydrothermal treatment time on the property of the resulting materials(such as phase composition and morphology)at different stages of preparation was conducted.Under the optimal conditions(i.e.,calcination temperature of 850℃,NaOH concentration of 3.3 mol·L^(-1),reaction temperature of 150℃,and reaction time of 6 h),a high-quality pure sodalite monolith was obtained,which possesses a relatively high BET surface area(58 m^(2)·g^(-1))and hierarchically micro-meso-macroporous structure.In the proposed application of continuous removal of heavy metals(chromium ion as the model)from wastewater,the developed 3D-printed sodalite monolith showed excellent Cr^(3+)removal performance and fast kinetics(~98%removal efficiency within 25 cycles),which outperformed the packed bed using sodalite pellets(made by extrusion).

Using ultrasound to improve the sequential post-synthesis modification method for making mesoporous Y zeolites

Mesoporous Y zeolites were prepared by the sequential chemical dealumination(using chelating agents such as ethylenediaminetetraacetic acid,H EDTA,and citric acid aqueous solutions)and alkaline desilication(using sodium hydroxide,NaOH,aqueous solutions)treatments.Specifically,the ultrasound-assisted alkaline treatment(i.e.,ultrasonic treatment)was proposed as the alternative to conventional alkaline treatments which are performed under hydrothermal conditions.In comparison with the hydrothermal alkaline treatment,the ultrasonic treatment showed the comparatively enhanced efficiency(with the reduced treatment time,i.e.,5 min vs.30 min,all with 0.2 mol·L NaOH at 65°C)in treating the dealuminated Y zeolites for creating mesoporosity.For example,after the treatment of a dealuminated zeolite Y(using 0.1 mol·L H EDTA at 100°C for 6 h),the ultrasonic treatment produced the mesoporous zeolite Y with the specific external surface area()of 160 m·g and mesopore volume()of 0.22 cm·g,being slightly higher than that by the conventional method(i.e.,=128 m·g and=0.19 cm·g).The acidic property and catalytic activity(in catalytic cracking of-octane)of mesoporous Y zeolites obtained by the two methods were comparable.The ultrasonic desilication treatment was found to be generic,also being effective to treat the dealuminated Y zeolites by citric acid.Additionally,the first step of chemical dealumination treatment was crucial to enable the effective creation of mesopores in the parent Y zeolite(with a silicon-to-aluminium ratio,Si/Al=2.6)regardless of the subsequent alkaline desilication treatment(i.e.,ultrasonic or hydrothermal).Therefore,appropriate selection of the condition of the chemical dealumination treatment based on the property of parent zeolites,such as Si/Al ratio and crystallinity,is important for making mesoporous zeolites effectively.

Electroactive barium titanate coated titanium scaffold improves osteogenesis and osseointegration with low-intensity pulsed ultrasound for large segmental bone defects

For large segmental bone defects,porous titanium scaffolds have some advantages,however,they lack electrical activity which hinders their further use.In this study,a barium titanate(BaTiO3)piezoelectric ceramic was used to modify the surface of a porous Ti6Al4V scaffold(pTi),which was characterized by scanning electron microscopy,energy dispersive spectroscopy,X-ray photoelectron spectroscopy,and roughness and water contact angle analyses.Low intensity pulsed ultrasound(LIPUS)was applied in vitro and in vivo study.The activity of bone marrow mesenchymal stem cells,including adhesion,proliferation,and gene expression,was significantly superior in the BaTiO3/pTi,pTi+LIPUS,and BaTiO3/pTi+LIPUS groups than in the pTi group.The activity was also higher in the BaTiO3/pTi+LIPUS group than in the BaTiO3/pTi and pTi+LIPUS groups.Additionally,micro-computed tomography,the mineral apposition rate,histomorphology,and the peak pull-out load showed that these scaffold conditions significantly enhanced osteogenesis and osseointegration 6 and 12 weeks after implantation in large segmental bone defects in the radius of rabbits compared with those resulting from the pTi condition.Consequently,the improved osteogenesis and osseointegration make the BaTiO3/pTi+LIPUS a promising method to promote bone regeneration in large segmental bone defects for clinical application.

Improved activity of MC3T3-E1 cells by the exciting piezoelectric BaTiO_(3)/TC4 using low-intensity pulsed ultrasound

Developing bioactive materials for bone implants to enhance bone healing and bone growth has for years been the focus of clinical research.Barium titanate(BT)is an electroactive material that can generate electrical signals in response to applied mechanical forces.In this study,a BT piezoelectric ceramic coating was synthesized on the surface of a TC4 titanium alloy,forming a BT/TC4 material,and low-intensity pulsed ultrasound(LIPUS)was then applied as a mechanical stimulus.The combined effects on the biological responses of MC3T3-E1 cells were investigated.Results of scanning electron microscopy,energy-dispersive X-ray spectroscopy,and X-ray diffraction showed that an uniform nanospheres-shaped BT coating was formed on TC4 substrate.Piezoelectric behaviors were observed using piezoelectric force microscopy with the piezoelectric coefficient d_(33)of 0.42 pC/N.Electrochemical measures indicated that LIPUS-stimulated BT/TC4 materials could produce a microcurrent of approximately 10μA/cm^(2).In vitro,the greatest osteogenesis(cell adhesion,proliferation,and osteogenic differentiation)was found in MC3T3-E1 cells when BT/TC4 was stimulated using LIPUS.Furthermore,the intracellular calcium ion concentration increased in these cells,possibly because opening of the L-type calcium ion channels was promoted and expression of the Ca_(V)1.2 protein was increased.Therefore,the piezoelectric BT/TC4 material with LIPUS loading synergistically promoted osteogenesis,rending it a potential treatment for early stage formation of reliable bone-implant contact.

A comparative study of Ni/Al_2O_3–SiC foam catalysts and powder catalysts for the liquid-phase hydrogenation of benzaldehyde

In this study, Al_2O_3-washcoated SiC(Al_2O_3–SiC) foams and Al_2O_3 powder were employed as the supports of a Ni catalyst for the liquid-phase hydrogenation of benzaldehyde. A series of Ni/Al_2O_3–SiC foam catalysts and Ni/Al_2O_3 powder catalysts with a Ni loading from 10 wt% to 37 wt% of the weight of Al_2O_3 were first prepared by a deposition–precipitation(DP) method. The catalytic activity and recyclability of both kinds of catalysts were then compared. Although it had a smaller accessible surface area with the reactant, the foam catalyst with a Ni loading of 16 wt% exhibited a slightly higher conversion of benzaldehyde after 6 h(of 99.3%) in comparison with the Ni/Al_2O_3 catalyst with identical Ni loading(conversion of 97.5%). When the Ni loading increased from 16 wt% to 37 wt%, the reaction rate obtained with the foam catalyst increased significantly from 0.108 to 0.204 mol L^(-1)h^(-1), whereas the reaction rate obtained with the powder catalyst increased from 0.106 to 0.123 mol L^(-1)h^(-1). Furthermore, the specific activity(moles of benzaldehyde consumed by 1 g min^(-1)of Ni) of the foam catalyst with a Ni loading above 30 wt% was superior to that of the powder catalyst because of its smaller Ni-particle size and higher mass-transfer rate. The foam catalyst displayed a high recyclability as a function of run times owing to the strong interaction between the Ni component and the Al_2O_3 coating. The conversion of benzaldehyde over the foam catalyst remained almost unchanged after being used 8 times. In comparison, a drop of 43% in the conversion of benzaldehyde with the powder catalyst was observed after being used 7 times due to the leaching of the Ni component.