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.

Functional zirconium phosphate nanosheets enabled transfer hydrogenolysis of aromatic ether bonds over a low usage of Ru nanocatalysts

Catalytic hydrogenolysis of aromatic ether bonds is a highly promising strategy for upgrading lignin into small-molecule chemicals,which relies on developing innovative heterogeneous catalysts with high activity.Herein,we designed porous zirconium phosphate nanosheet-supported Ru nanocatalysts(Ru/ZrPsheet)as the heterogeneous catalyst by a process combining ball milling and molten-salt(KNO_(3)).Very interestingly,the fabricated Ru/ZrPsheetshowed good catalytic performance on the transfer hydrogenolysis of various types of aromatic ether bonds contained in lignin,i.e.,4-O-5,a-O-4,β-O-4,and aryl-O-CH3,over a low Ru usage(<0.5 mol%)without using any acidic/basic additive.Detailed investigations indicated that the properties of Ru and the support were indispensable.The excellent activity of Ru/ZZrPsheetoriginated from the strong acidity and basicity of ZrPsheetand the higher electron density of metallic Ru0as well as the nanosheet structure of ZrPsheet.

Complete degradation of high-loaded phenol using tungstate-based ionic liquids with long chain substituent at mild conditions

Phenol in waste water threatens human health and is difficultly to be decomposed by nature.Efficient degradation of high-loaded phenol in water under mild condition is still a great challenge.Herein,ionic liquids with tungstate anion were designed and prepared.It was found that dodecyltrimethylammonium tungstate could catalyzed degradation of phenol into gases and water thoroughly at 323 k in 8 h.Tungstate anion revealed good catalytic oxidative activity and long carbon chain group connecting with cation of ionic liquids enriched phenol around catalysts,which induced the complete degradation of phenol at mild conditions.Increasing the amounts of hydrogen peroxide benefited to the total degradation of phenol.In addition,the ionic liquid could be reused for its excellent thermal stability.Our work provided a different strategy to treat waste water containing phenol efficiently.

Acidichromism in the LB film of bolaform Schiff base

bolaform (BNC10 ) 并且领导单人赛(HNOA ) 包含 naphthyl 组的 amphiphilic Schiff 被设计，他们的 Langmuir Blodgett 电影被调查。两个都， LB 电影显示出 acidichromism，这被发现，即在或者分别地暴露这些电影到 HCl 和 NH3 气体之上的可逆变色。bolaform Schiff 电影能在 acidichromic 过程期间套住 NH3 气体，这进一步被发现。

Applying dynamic light scattering to investigate the self-assembly process of DNA nanostructures

Understanding the dynamic assembly process of DNA nanostructures is important for developing novel strategy to design and construct functional devices.In this work,temperature-controlled dynamic light scattering(DLS)strategy has been applied to study the global assembly process of DNA origami and DNA bricks.Through the temperature dependent size and intensity profiles,the self-assembly process of various DNA nanostructures with different morphologies have been well-studied and the temperature transition ranges could be observed.Taking advantage of the DLS information,rapid preparation of the DNA origami and the brick assembly has been realized through a constant temperature annealing.Our results demonstrate that the DLS-based strategy provides a convenient and robust tool to study the dynamic process of forming hieratical DNA structures,which will benefit understanding the mechanism of self-assembly of DNA nanostructures.

Enhanced CO_(2)electroreduction to ethylene via strong metal-support interaction

The CuO/CeO_(2) composites with strong metal-support interaction were synthesised,which can efficiently electroreduct CO_(2)to C(2)H_(4).The Faradaic efficiency(FE)of C_(2)H_(4) could reach 50.5%with a current density of 18 mA cm^(-2).The strong metal-support interaction could not only enhance the adsorption and activation of CO_(2),but also can stablize the CuO.

Controllable oxygen vacancies and morphology engineering:Ultra-high HER/OER activity under base–acid conditions and outstanding antibacterial properties

Introducing vacancy defects and unique morphology is an effective strategy to improve the catalytic performance of transition metal compounds.However,precisely controlling the amount of vacancy defects remains challenging.Here,we propose a facile and efficient hydrothermal accompanying an annealing method to synthesize a series of Mn-doped CoO nanomaterials with controllable oxygen vacancies and unique morphology.The oxygen vacancies amount can be precisely controlled by adjusting the Mndoping content and is positively correlated with catalytic performance.It was found that the oxygen vacancies amount can reach up to 38.2%over the Mn-doped CoO nanomaterials,resulting in ultra-high hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalytic activity(HER:25.6 and 37 m V at 10 m A cm^(-2);OER:301 and 322 m V at 50 m A cm^(-2))under both basic and acidic conditions,while reaching 10 m A cm^(-2) for an ultra-low cell voltage of only 1.52 V,which exceeds that of Pt/C/RuO_(2) and all reported non-noble metal oxide catalysts.The DFT calculations reveal oxygen vacancies can optimize H*and HOO*intermediates adsorption free energy,thus improving the HER and OER performance.Interestingly,the Mn-doped CoO with rich oxygen vacancies exhibits excellent antibacterial properties in vitro of biomedicine.This work provides new ideas and methods for the rational design and precise control of vacancy defects in transition metal compounds and explores their potential application value in electrochemical water splitting and biomedical fields.

Ferric acetylacetonate/covalent organic framework composite for high performance photocatalytic oxidation

Ferric acetylacetonate/covalent organic framework(Fe(acac)_(3)/COF)composite was synthesized by interfacial polymerization method at room temperature.The crystal structure,morphology and porosity property of the composite were characterized by X-ray diffraction,scanning electron microscope,transmission electron microscope and nitrogen adsorption.The interaction between Fe(acac)_(3) and COF was investigated by Fourier transform infrared spectra and X-ray photoelectron spectroscopy.The Fe(acac)_(3)/COF composite was used as a photocatalyst for the oxidation of benzyl alcohol under mild conditions.It exhibits high activity and selectivity for the reaction,of which the mechanism was investigated by determining its photoelectric properties.The Fe(acac)_(3)/COF catalyst developed in this work has application potential in other photocatalytic reactions.

二维材料最新研究进展

Research on two-dimensional(2D) materials has been explosively increasing in last seventeen years in varying subjects including condensed matter physics, electronic engineering, materials science, and chemistry since the mechanical exfoliation of graphene in 2004. Starting from graphene, 2D materials now have become a big family with numerous members and diverse categories. The unique structural features and physicochemical properties of 2D materials make them one class of the most appealing candidates for a wide range of potential applications. In particular, we have seen some major breakthroughs made in the field of 2D materials in last five years not only in developing novel synthetic methods and exploring new structures/properties but also in identifying innovative applications and pushing forward commercialisation. In this review, we provide a critical summary on the recent progress made in the field of 2D materials with a particular focus on last five years. After a brief backgroundintroduction, we first discuss the major synthetic methods for 2D materials, including the mechanical exfoliation, liquid exfoliation, vapor phase deposition, and wet-chemical synthesis as well as phase engineering of 2D materials belonging to the field of phase engineering of nanomaterials(PEN). We then introduce the superconducting/optical/magnetic properties and chirality of 2D materials along with newly emerging magic angle 2D superlattices. Following that, the promising applications of 2D materials in electronics, optoelectronics, catalysis, energy storage, solar cells, biomedicine, sensors, environments, etc. are described sequentially. Thereafter, we present the theoretic calculations and simulations of 2D materials. Finally, after concluding the current progress, we provide some personal discussions on the existing challenges and future outlooks in this rapidly developing field.

Water-mediated phase-change composite electrolyte

With the world's focus on wearable electronics, the scientific community has anticipated the plasticine-like processability of electrolytes and electrodes. A bioinspired composite of polymer and phase-changing salt with the similar bonding structure to that of natural bones is a suitable electrolyte candidate. Here, Wang et al. reported a water-mediated composite electrolyte by simple thermal mixing of crystallohydrate and polymer. The processable phase-change composites have significantly high mechanical strength and high ionic mobility.

Ultra-small UiO-66-NH_(2)nanoparticles immobilized on g-C_(3)N_(4)nanosheets for enhanced catalytic activity

UiO-66-NH_(2),an important metal-organic framework,is usually synthesized by solvothermal method and the particle size is generally larger than 200 nm,which limits its catalytic applications in chemical reactions.It is very meaningful to produce UiO-66-NH_(2) nanoparticles with ultrasmall size,but remains challenging.Herein,we synthesized UiO-66-NH_(2) nanoparticles in size of 8-15 nm that are immobilized on g-C_(3)N_(4)nanosheets.Compared with the UiO-66-NH_(2) synthesized by the traditional solvothermal method(>200 nm),the ultra-small UiO-66-NH_(2) nanoparticles immobilized on g-C_(3)N_(4)have more unsaturated coordination positions and increased Lewis acidity.Owing to these combined advantages,the ultra-small UiO-66-NH_(2)nanoparticles exhibit greatly improved catalytic activity for Meerwein-Ponndorf-Verley reaction than larger UiO-66-NH_(2)particles.

Preparation of Photo-responsive DNA Supramolecular Hydrogels and Their Application as UV Radiometers

Ultraviolet light(UV)is an essential component of ambient light,but high dose UV would damage genome DNA.While semiconductors and soft materials have been employed to detect the UV,the complex process and the instrumental requirement have limited the application in daily life.In this study,taking advantage of sequence designability,a series of hydrogels with different gel-sol transition rates was constructed under the same UV intensity by introducing competing hybridization to tune the stability of the molecular network.Through estimating the transition time between each system under UV light irradiation,the intensity of UV could be roughly estimated,which provided a convenient method for the visual detection of UV.

Atomically Dispersed Pt and NiO Clusters Synergistically Enhanced C–O Bond Hydrogenolysis

C–Obond activation is a highly efficient,fundamental strategy in the depolymerization and hydrodeoxygenation of chemicals with oxygen-containing functional groups such as oil,coal,and biomass.Developing efficient catalysts for C–Oactivation with ultralow-loading noble and non-noble metals is highly desirable for the improvement of metal atomic utilization.Herein,bimetallic catalysts with atomically dispersed Pt and NiO clusters on different supports were fabricated,and the prepared Pt^(δ+)-NiO/Nb_(2)O_(5)and Pt^(δ+)-NiO/TiO_(2)showed outstanding activity for the hydrogenolysis of benzyl phenyl ether with>99%yield of phenol and toluene due to the excellent cooperation of atomically dispersed Pt and NiO clusters.The synergy mechanism between Pt and Ni and their respective roles in the bimetallic catalyst for C–O hydrogenolysis were clearly clarified.These findings deepen our understanding of the synergy of the two active components and are expected to provide new design concepts for the development of multicomponents catalysts.

Electrochemical reduction of CO_2 to CO using graphene oxide/carbon nanotube electrode in ionic liquid/acetonitrile system

Electrochemical reduction of CO_2 to CO is an interesting topic. In this work, we prepared metal-free electrodes by depositing graphene oxide(GO), multi-walled carbon nanotube(MWCNT), and GO/MWCNT composites on carbon paper(CP) using electrophoretic deposition(EPD) method. The electrodes were characterized by different methods, such as X-ray diffraction(XRD) and X-ray photoelectron spectroscopy(XPS). The electrochemical reduction of CO_2 to CO was conducted on the electrodes in 1-butyl-3-methylimidazolium tetrafluoroborate([Bmim]BF4)/acetonitrile(Me CN) electrolyte, and the composition of the electrolyte influenced the reaction significantly. It was demonstrated that GO/MWCNT-CP electrode was very effective for the reaction in IL(90 wt%)/Me CN binary mixture, the Faradaic efficiency of CO and current density were even higher than those on Au and Ag electrodes in the same electrolyte.

Ethylenediamine promoted the hydrogenative coupling of nitroarenes over Ni/C catalyst

Azobenzene and its derivatives are key raw materials and it is an environmentally friendly method for the preparation of azobenzene by hydrogenative coupling of nitrobenzene. The development of nickel based catalyst for organic transformations is of importance because of its relatively low cost and toxicity. In this work, we found that ethylenediamine can enrich the electron state of Ni and make the azobenzene easily desorb from the surface of the catalyst, which inhibits the hydrogenation of azobenzene to aniline. The selectivity of azobenzene is greatly improved. When the ratio of Ni and ethylenediamine is 1:10, the yield of the azobenzene can reach 95.5%.

Basic ionic liquids promoted chemical transformation of CO_2 to organic carbonates

Ionic liquids(ILs), especially basic ILs with unique physicochemical properties, have wide application in catalysis. Using basic ILs as catalysts for the conversion of cheap, abundant, nontoxic, and renewable CO_2 into value-added organic carbonates is highly significant in view of environmental and economic issues. This review aims at giving a detailed overview on the recent advances on basic ILs promoted chemical transformation of CO_2 to cyclic and linear carbonates. The structures of various basic ILs, as well as the basic ILs promoted reactions for the transformation of CO_2 to organic carbonates are discussed in detail,including the reaction conditions, the yields of target products, the catalytic activities of basic ILs and the reaction mechanism.

Nitrogen-carbon layer coated nickel nanoparticles for efficient electrocatalytic reduction of carbon dioxide

The application of nickel in electrocatalytic reduction of CO2 has been largely restricted by side reaction (hydrogen evolution reaction) and catalyst poisoning.Here we report a new strategy to improve the electrocatalytic performance of nickel for CO2 reduction by employing a nitrogen-carbon layer for nickel nanoparticles.Such a nickel electrocatalyst exhibits high Faradaic efficiency 97.5% at relatively low potential of-0.61 V for the conversion of CO2 to CO.Density functional theory calculation reveals that it is thermodynamically accomplishable for the reduction product CO to be removed from the catalyst surface,thus avoiding catalyst poisoning.Also,the catalyst renders hydrogen evolution reaction to be suppressed and hence reasonably improves catalytic performance.

Selective electroreduction of carbon dioxide to formic acid on electrodeposited SnO_2@N-doped porous carbon catalysts

Electrocatalytic reduction of CO_2 is a promising route for energy storage and utilization. Herein we synthesized SnO_2 nanosheets and supported them on N-doped porous carbon (N-PC) by electrodeposition for the first time. The SnO_2 and N-PC in the SnO_2@N-PC composites had exellent synergistic effect for electrocatalytic reduction of CO_2 to HCOOH. The Faradaic efficiency of HCOOH could be as high as 94.1% with a current density of 28.4 mA cm-2 in ionic liquid-MeCN system. The reaction mechanism was proposed on the basis of some control experiments. This work opens a new way to prepare composite electrode for electrochemical reduction of CO_2.

Preparation of optical active polydiacetylene through gelating and the control of supramolecular chirality

Achiral diacetylene 10,12-pentacosadinoic acid (PCDA) and a chiral low-molecular-weight organogelator could form co-gel in organic solvent and it could be polymerized in the presence of Zn(II) ion or in the corresponding xerogel under UV-irradiation. Optically active polydiacetylene (PDA) were subsequently obtained. Supramolecular chirality of PDA could be controlled by the chirality of gelators. Left-handed and right-handed helical fibers were obtained by using Land D-gelators in xerogels respectively, and CD spectra exhibited mirror-image circular dichroism. The PDA in xerogel exhibited typical blue-to-red transition responsive to the temperature and pH, while the supramolecular chirality of PDA showed a corresponding change.