Catalytic performance of acidic ionic liquid-functionalized silica in biodiesel production

Acidic ionic liquid([BsAIm][OTf]) was immobilized on sulfhydryl-group-modified SiO2(MPS-SiO2) via free radical addition reaction. The[BsAIm][OTf] loading on acidic ionic liquid-functionalized silica([BsAIm][OTf]/SiO2) was controlled through tuning the sulfydryl(SH)content of MPS-SiO2. All the samples were characterized by FT-IR, elemental analysis, N2adsorption-desorption measurements and TGDTA. The catalytic performance of [BsAIm][OTf]/SiO2in the esterification of oleic acid and the transesterification of glycerol trioleate for biodiesel production was investigated. The results showed that with the increase of [BsAIm][OTf] loading on SiO2the specific surface area and pore volume of [BsAIm][OTf]/SiO2decreased, and the pore diameter of [BsAIm][OTf]/SiO2narrowed. In the esterificaiton of oleic acid, the oleic acid conversion increased with the increasing [BsAIm][OTf] loading. In the transesterification of glycerol trioleate, with the increasing[BsAIm][OTf] loading the glycerol trioleate conversion decreased and the selectivities to glycerol monooleate and methyl oleate increased.

Preparation of water-soluble magnetic nanoparticles with controllable silica coating

This work provides a general method for preparing monodisperse, water-soluble and paramagnetic magnetic nanoparticles which are easy to be modified. Firstly, magnetic silica with core-shell structure was prepared according to a previous work. Then, the magnetic silica was treated with alkali solution to afford magnetic nanoparticles. With the increase of calcination temperature for the preparation of magnetic silica, the crystallinity and the magnetic responsibility of magnetic silica strengthened, meanwhile, the corresponding magnetic nanoparticles kept monodisperse without any aggregation. The magnetic nanoparticles are comprised of cobalt ferrite and a silica coating. The silica coating on the cobalt ferrite facilitates the magnetic nanoparticles well-dissolved and monodisperse in water, and easilv modified.

Enhanced charge separation by incomplete calcination modified co-doped TiO_(2)nanoparticle for isothiazolinone photocatalytic degradation

Photocatalytic oxidation techniques are promising for degradation of the highly ecotoxic and refractory isothiazolinone bactericides in relevant industrial wastewaters.However,low charge separation and directional transport efficiency under solar light radiation restrain their practical application.Here,we report a nanostructured photocatalyst doped with Gd and B in TiO_(2)with carbon incorporation and defect formation through incomplete calcination.The specific surface area,grain size,and hydrophilicity of TiO_(2)are improved,which is beneficial for the interfacial reaction between the photocatalyst and pollutants.The reduction of the bandgap,the broadening of the photo-absorption range,and the retarded electron-hole recombination promote the photocatalytic performance due to the improved oxygen vacancies based on the electron distribution modification.The difference in partial density of states(ΔPDOS)between the current catalyst and raw TiO_(2)indicates that the co-doping of Gd and B with incomplete calcination changes the electronic hybridization of conduction band and valence band near the Fermi level,and affects the band gap energy.It improved charge separation and directional transport efficiency and benefited the formation of main active species,including•OH and O_(2)•−,for the pollutant decomposition.The rate of photocatalytic removal of benzisothiazolinone(BIT)by the current photocatalyst reaches 1.25 h^(−1),being 4.31 times that of TiO_(2).The current work offers a constructive approach to the design and synthesis of nanostructured photocatalysts for the photocatalytic degradation of refractory organic pollutants.

Rational Construction of Hierarchically Porous Fe–Co/N-Doped Carbon/rGO Composites for Broadband Microwave Absorption

Developing lightweight and broadband microwave absorbers for dealing with serious electromagnetic radiation pollution is a great challenge.Here,a novel Fe-Co/N-doped carbon/reduced graphene oxide(Fe-Co/NC/rGO)composite with hierarchically porous structure was designed and synthetized by in situ growth of Fe-doped Cobased metal organic frameworks(Co-MOF)on the sheets of porous cocoon-like rGO followed by calcination.The Fe-Co/NC composites are homogeneously distributed on the sheets of porous rGO.The Fe-Co/NC/rGO composite with multiple components(Fe/Co/NC/rGO)causes magnetic loss,dielectric loss,resistance loss,interfacial polarization,and good impedance matching.The hierarchically porous structure of the Fe-Co/NC/rGO enhances the multiple reflections and scattering of microwaves.Compared with the Co/NC and Fe-Co/NC,the hierarchically porous Fe-Co/NC/rGO composite exhibits much better microwave absorption performances due to the rational composition and porous structural design.Its minimum reflection loss(RLmin)reaches?43.26 dB at 11.28 GHz with a thickness of 2.5 mm,and the effective absorption frequency(RL≤?10 dB)is up to 9.12 GHz(8.88-18 GHz)with the same thickness of 2.5 mm.Moreover,the widest effective bandwidth of 9.29 GHz occurs at a thickness of 2.63 mm.This work provides a lightweight and broadband microwave absorbing material while offering a new idea to design excellent microwave absorbers with multicomponent and hierarchically porous structures.

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.

Methane reforming with CO_2 to syngas over CeO_2-promoted Ni/Al_2O_3-ZrO_2 catalysts prepared via a direct sol-gel process

CeO2-promoted Ni/Al2O3-ZrO2 （Ni/Al2O3-ZrO2-CeO2） catalysts were prepared by a direct sol-gel process with citric acid as gelling agent. The catalysts used for the methane reforming with CO2 was studied by infrared spectroscopy （IR）, thermal gravimetric analysis （TGA）, microscopic analysis, X-ray diffraction （XRD） and temperature-programmed reduction （TPR）. The catalytic performance for CO2 reforming of methane to synthesis gas was investigated in a continuous-flow micro-reactor under atmospheric pressure. TGA, IR, XRD and microscopic analysis show that the catalysts prepared by the direct sol-gel process consist of Ni particles with a nanostructure of around 5 nm and an amorphous-phase composite oxide support. There exists a chemical interaction between metallic Ni particles and supports, which makes metallic Ni well dispersed, highly active and stable. The addition of CeO2 effectively improves the dispersion and the stability of Ni particles of the prepared catalysts, and enhances the adsorption of CO2 on the surface of catalysts. The catalytic tests for methane reforming with CO2 to synthesis gas show that the Ni/Al2O3-ZrO2-CeO2 catalysts show excellent activity and stability compared with the Ni/Al2O3 catalyst. The excellent catalytic activity and stability of the Ni/Al2O3-ZrO2-CeO2 are attributed to the highly, uniformly and stably dispersed small metallic Ni particles, the high reducibility of the Ni oxides and the interaction between metallic Ni particles and the composite oxide supports.

In-situ growth of low-dimensional perovskite-based insular nanocrystals for highly efficient light emitting diodes

Regulation of perovskite growth plays a critical role in the development of high-performance optoelectronic devices.However,judicious control of the grain growth for perovskite light emitting diodes is elusive due to its multiple requirements in terms of morphology,composition,and defect.Herein,we demonstrate a supramolecular dynamic coordination strategy to regulate perovskite crystallization.The combined use of crown ether and sodium trifluoroacetate can coordinate with A site and B site cations in ABX_(3) perovskite,respectively.The formation of supramolecular structure retard perovskite nucleation,while the transformation of supramolecular intermediate structure enables the release of components for slow perovskite growth.This judicious control enables a segmented growth,inducing the growth of insular nanocrystal consist of low-dimensional structure.Light emitting diode based on this perovskite film eventually brings a peak external quantum efficiency up to 23.9%,ranking among the highest efficiency achieved.The homogeneous nano-island structure also enables high-efficiency large area(1 cm^(2))device up to 21.6%,and a record high value of 13.6%for highly semi-transparent ones.

Band alignment towards high-efficiency NiOx-based Sn-Pb mixed perovskite solar cells

Narrow-bandgap tin-lead(Sn-Pb)mixed perovskite solar cells(PSCs)play a key role in constructing perovskite tandem solar cells that are potential to overpass Shockley-Queisser limit.A robust,chemically stable and lowtemperature-processed hole transporting layer(HTL)is essential for building high-efficiency Sn-Pb solar cells and perovskite tandem solar cells.Here,we explore a roomtemperature-processed NiOx(L-NiOx)HTL based on nanocrystals(NCs)for Sn-Pb PSCs.In comparison with hightemperature-annealed NiOx(H-NiOx)film,the L-NiOx film shows deeper valence band and lower trap density,which increases the built-in potential and reduces carrier recombination,leading to a power conversion efficiency of 18.77%,the record for NiOx-based narrow-bandgap PSCs.Furthermore,the device maintains about 96%of its original efficiency after 50 days.This work provides a robust and room-temperatureprocessed HTL for highly efficient and stable narrow-bandgap PSCs.

Tin Halide Perovskite Solar Cells:An Emerging Thin-Film Photovoltaic Technology

Perovskite semiconductors are regarded as nextgeneration photovoltaic materials owing to their superb optoelectronic properties,including an excellent carrier diffusion length,strong light absorbption,low defect density,and solution processability.The PCE of lead perovskite solar cells(LPSC)rapidly increased from 3.8 to 25.5%in the past decade.However,the inclusion of soluble,toxic lead shadows its application due to environmental concerns.Furthermore,on the basis of the Shockley−Quisser(S−Q)limit,the efficiency of lead perovskite is limited to 32%since its band gap is>1.5 eV.To increase the efficiency of perovskite solar cells further,perovskite materials with a smaller band gap are required.Tin halide perovskite is currently the most promising alternative candidate that can address the above challenges due to its potentially less toxic character and electronic configuration analogous to that of lead.Its band gap(sub-1.4 eV)is lower than that of lead perovskite,approaching the ideal band gap with a theoretical efficiency of up to 33.4%based on the S−Q equation.However,tin perovskite is extremely easy to oxidize due to its unique electronic structure.Early works focus on the development of methods to reduce tin oxidation such as the addition of antioxidant additives or using low-dimensional structures.On the basis of these strategies,the reproducibility and efficiency of TPSCs have been significantly improved.In recent years,many works including composition engineering,functional additives,and device structure engineering have been used to improve the performance of TPSCs.On the basis of these strategies,the open-circuit voltage is improved to 0.94 V and the PCE certified by an independent laboratory is up to 12.4%.Meanwhile,the stability of TPSCs is significantly improved,and the stabilized power output time is up to 1000 h.Therefore,tin perovskite is emerging as a new generation of low-cost thin-film photovoltaic technology.This Account summarizes the properties of tin halide perovskites and the material and device engineering strategies toward more efficient and stable TPSCs.We highlight the unique properties of tin perovskites that distinguish them from lead perovskites,including their electronic structure,band structure,chemical properties,and so on.We discuss the critical challenges for the further development of TPSCs such as oxidation,high background carriers,uncontrollable crystallization,interface recombination,band alignment,and instability.In the end,we introduce potential directions for the future development of TPSCs including probing the formation mechanisms of tin perovskite,revealing the basic properties of Sn perovskite,overcoming the stability issue of TPSCs,and understanding TPSC device physics and structure engineering.

High-member low-dimensional Sn-based perovskite solar cells

Sn-based perovskites are promising thin-film photovoltaic materials for their ideal bandgap and the eco-friendliness of Sn,but the performance of Sn-based perovskite solar cells is hindered by the short carrier diffusion length and large defect density in nominally-synthesized Sn-based perovskite films.Herein we demonstrate that a long carrier diffusion length is achievable in quasi-2D Sn-based perovskite films consisting of high-member low-dimensional Ruddlesden-Popper(RP)phases with a preferred crystal orientation distribution.The key to the film synthesis is the use of a molecular additive formed by phenylethylammonium cations and optimally mixed halide-pseudohalide anions,which favorably tailors the quasi-2D Sn-based perovskite crystallization kinetics.The high-member RP film structure effectively enhances device short-circuit current density,giving rise to an increased power conversion efficiency(PCE)of 14.6%.The resulting device demonstrates a near-unity shelf stability upon1,000 h in nitrogen.A high reproductivity is also achieved with a count of 50 devices showing PCEs within a narrow range from minimum 13.0%to maximum 14.6%.