Promotion of GSC Technology Innovation by the Green and Sustainable Chemistry Network

The Green and Sustainable Chemistry Network （GSCN） has been promoting GSC technology development since 2000 in three major activities, holding the GSC symposium, running the GSC Awards, and providing the information related to GSC in Japan. GSCN holds a vision to expand the philosophy of GSC not only to the domestic, but also to the global. As for a regional network in Asia and Oceania, we established the Asia-Oceania GSC Network, and we hope to expand the Network to all countries.

The energy-chemistry nexus: A vision of the future from sustainability perspective

The changing energy-chemistry nexus is discussed in this perspective paper about the future of sustainable energy and chemical production to identify the priorities and open issues on which focus research and development. Topics discussed regard （i） the new sustainable energy scenario, （ii） the role of energy storage （from smart grids to chemical storage of energy）, （iii） the outlooks and role of solar （bio）refineries and solar fuels, （iv） how to integrate hio- and solar-refineries to move to new economy, （v） the role of methanol at the crossover of new energy-chemistry nexus, （vi） the role of chemistry in this new scenario, （vii） the role of nanomaterials for a sustainable energy, （viii） the use of nanocarbons to design advanced energy conversion and storage devices, and （ix） possibilities and routes to exploit solar energy and methane （shale gas）. The contribution provides a glimpse of the emerging directions and routes with some elements about their possible role in the future scenario, but does not orovide a detailed analysis of the state of the art in these directions

Reviewing electrochemical stability of ionic liquids-/deep eutectic solvents-based electrolytes in lithium-ion,lithium-metal and post-lithium-ion batteries for green and safe energy

Sustainable energy is the key issue for the environment protection,human activity and economic development.Ionic liquids(ILs)and deep eutectic solvents(DESs)are dogmatically regarded as green and sustainable electrolytes in lithium-ion,lithium-metal(e.g.,lithium-sulphur,lithium-oxygen)and post-lithium-ion(e.g.,sodium-ion,magnesium-ion,and aluminum-ion)batteries.High electrochemical stability of ILs/DESs is one of the prerequisites for green,sustainable and safe energy;while easy electrochemical decomposition of ILs/DESs would be contradictory to the concept of green chemistry by adding the cost,releasing volatile/hazardous by-products and hindering the recyclability.However,(1)are ILs/DESs-based electrolytes really electrochemically stable when they are not used in batteries?(2)are ILs/DESs-based electrolytes really electrochemically stable in real batteries?(3)how to design ILs/DESs-based electrolytes with high electrochemical stability for batteries to achieve sustainability and green development?Up to now,there is no summary on this topic,to the best of our knowledge.Here,we review the effect of chemical structure and non-structural factors on the electrochemical stability of ILs/DESs in simulated conditions.More importantly,electrochemical stability of ILs/DESs in real lithium-ion,lithium-metal and post-lithium-ion batteries is concluded and compared.Finally,the strategies to improve the electrochemical stability of ILs/DESs in lithium-ion,lithium-metal and post-lithium-ion batteries are proposed.This review would provide a guide to design ILs/DESs with high electrochemical stability for lithium-ion,lithium-metal and postlithium-ion batteries to achieve sustainable and green energy.

A sulfur self-doped multifunctional biochar catalyst for overall water splitting and a supercapacitor from Camellia japonica flowers

A versatile use of a sulfur self-doped biochar derived from Camellia japonica(camellia)flowers is demonstrated as a multifunctional catalyst for overall water splitting and a supercapacitor.The native sulfur content in the camellia flower facilitates in situ self-doping of sulfur,which highly activates the camellia-driven biochar(SA-Came)as a multifunctional catalyst with the enhanced electron-transfer ability and long-term durability.For water splitting,an SA-Came-based electrode is highly stable and shows reaction activities in both hydrogen and oxygen evolution reactions,with overpotentials of 154 and 362 mV at 10 mA cm^(−2),respectively.For supercapacitors,SA-Came achieves a specific capacitance of 125.42 F g^(−1)at 2 A g^(−1)and high cyclic stability in a three-electrode system in a 1 M KOH electrolyte.It demonstrated a high energy density of 34.54 Wh kg^(−1)at a power density of 1600 W kg^(−1)as a symmetric hybrid supercapacitor device with a wide working potential range of 0-1.6 V.

Transformations of biomass-based levulinate ester into γ-valerolactone and pyrrolidones using carbon nanotubes-grafted N-heterocyclic carbene ruthenium complexes

As a renewable biomass-based compound with wide applications in food additives,fine chemical synthesis and fuels,γ-valerolactone(GVL)has attached much attention.While,pyrrolidones are widely used in pharmaceutical,agrochemical,material industrial and other chemical production.In this research,we demonstrated transformations of biomass-based ethyl levulinate(EL)into GVL and pyrrolidones by using heterogeneous catalysts(CNT-Ru-1)with N-heterocyclic carbene ruthenium(NHC-Ru)complex grafted on multi-walled carbon nanotube(CNT).The Ru catalyst showed high efficiency on EL hydrogenation to GVL with both EL conversion and GVL yield exceeding 99%.Moreover,the Ru catalyst readily promoted reductive amination of EL in the presence of various amines for pyrrolidone synthesis.Finally,the Ru catalyst was also applicable to hydrogenation of various carbonyl compounds for the synthesis of the corresponding alcohols with excellent catalytic performance.The research provides insight for heterogenizing the homogeneous noble metal-based catalysts with high catalytic active for biomass-based transformations.

Surface reconstruction,modification and functionalization of natural diatomites for miniaturization of shaped heterogeneous catalysts

Since the discovery of mesoporous silica in 1990s,there have been numerous mesoporous silica-based nanomaterials developed for catalytic applications,aiming at enhanced catalytic activity and stability.Recently,there have also been considerable interests in endowing them with hierarchical porosities to overcome the diffusional limitation for those with long unimodal channels.Present processes of making mesoporous silica largely rely on chemical sources which are relatively expensive and impose environmental concerns on their processes.In this regard,it is desirable to develop hierarchical silica supports from natural minerals.Herein,we present a series of work on surface reconstruction,modification,and functionalization to produce diatomite-based catalysts with original morphology and macro-meso-micro porosities and to test their suitability as catalyst supports for both liquid-and gas-phase reactions.Two wet-chemical routes were developed to introduce mesoporosity to both amorphous and crystalline diatomites.Importantly,we have used computational modeling to affirm that the diatomite morphology can improve catalytic performance based on fluid dynamics simulations.Thus,one could obtain this type of catalysts from numerous natural diatoms that have inherently intricate morphologies and shapes in micrometer scale.In principle,such catalytic nanocomposites acting as miniaturized industrial catalysts could be employed in microfluidic reactors for process intensification.

Acidic Magnetic Biocarbon-Enabled Upgrading of Biomass-Based Hexanedione into Pyrroles

Sustainable acquisition of bioactive compounds from biomass-based platform molecules is a green alternative for existing CO_(2)-emitting fossil-fuel technologies.Herein,a core–shell magnetic biocarbon catalyst functionalized with sulfonic acid(Fe3O4@SiO_(2)@chitosan-SO_(3)H,MBC-SO_(3)H)was prepared to be efficient for the synthesis of various N-substituted pyrroles(up to 99% yield)from bio-based hexanedione and amines under mild conditions.The abundance of Bronsted acid sites in the MBC-SO_(3)H ensured smooth condensation of 2,5-hexanedione with a variety of amines to produce N-substituted pyrroles.The reaction was illustrated to follow the conventional Pall-Knorr coupling pathway,which includes three cascade reaction steps:amination,loop closure and dehydration.The prepared MBC-SO_(3)H catalyst could effectively activate 2,5-hexanedione,thus weakening the dependence of the overall conversion process on the amine nucleophilicity.The influence of different factors(e.g.,reaction temperature,time,amount of catalyst,molar ratio of substrates,and solvent type)on the reaction activity and selectivity were investigated comprehensively.Moreover,the MBC-SO_(3)H possessed excellent thermochemical stability,reusability,and easy separation due to the presence of magnetic core-shell structures.Notably,there was no activity attenuation after 5 consecutive catalytic experiments.This work demonstrates a wide range of potential applications of developing functionalized core-shell magnetic materials to construct bioactive backbones from biomass-based platform molecules.

Porous carbon catalysis in sustainable synthesis of functional heterocycles:An overview

Heterogeneous porous carbon(PC)materials have gained unique importance in the catalysis community due to their captivating properties,including high specific surface area,tunable porosity,and function-ality.PC can play a prominent role in the sustainable synthesis of functional heterocycles,as they are a low-cost alternative while being an efficient and user-friendly material.This review examines the prepa-ration and applicability of these carbonaceous materials used as catalysts or support for biologically active heterocycles synthesis,including hydrogenation,oxidation,oxidative dehydrogenation,cross-coupling,and other organic reactions.Moreover,the challenges,potential future development directions,and opportuni-ties in the synthesis of potent bioactive heterocycles over PC materials have been addressed.This review will inspire further research to explore novel PC materials and their implications in heterocyclization.

Carbonylative transformation of aryl halides and strong bonds via cheap metal catalysts and sustainable technologies

The development of catalytic carbonylation reactions has increased considerably.Although many reviews/chapters/books on carbonylation reactions have been published,summaries on cheap metal-catalyzed catalytic carbonylation reactions of aryl halides and other chemical bonds with high dissociation energy C–Y(Y=O,N,H)are still very rare.Focusing on green and sustainable chemistry,this review summarizes and discusses the achievements on carbonylative transformations of aryl halides(C(sp^(2))–X)and strong bonds C–Y(Y=O,N,H)based on non-expensive metal catalysts(Co,Mn,Mo,Ni,Fe,Cu),photochemical and electrochemical systems developed in recent decades.

Sensitivity and Compatibility Analysis of Sulfur and Phosphorus Type Additives in Rapeseed Oil

The effects of sulfur type additives T321 and phosphorous type additives P120 on the EP and AW abilities of rapeseed oil were investigated by a four-ball testing machine using the rapeseed oil as base oil.The effect of T321 mixed with P120 on the tribochemical performance of the rapeseed oil was studied.The result shows that the load carrying,extreme pressure and abrasion capacities of lubricant film can be improved by adding T321 and P120 as additives in rapeseed oil, respectively. The SEDX analysis on the surface of steel balls reveals that tribochemical reactions occur during the friction process, the barrier lubricating film is formed containing triglyceride and the additives can improve the anti-wear ability and load-carrying capacity.

Merging cobalt catalysis and electrochemistry in organic synthesis

There is an increasing demand of using the low-cost and sustainable cobalt to replace its noble congeners(rhodium and iridium)as reflected by the recent upsurge of cobalt catalysis in the diverse organic transformations.Since all the redox reactivity of cobalt catalysis highly relies on the capability of the interconversion between their oxidation states(most frequently+1,+2 and+3),electrochemistry perfectly meets such a require ment owing to its outstanding perfo rmance in the redox manipulation.In this review,we highlight the recent advances in the merger of cobalt catalysis and electrochemistry in organic synthesis.

In Situ Formation of Frustrated Lewis Pairs in a Zirconium Metal-Organic Cage for Sustainable CO_(2)Chemical Fixation

Sustainable CO_(2)fixation represents a facile and promising approach to constructing various valueadded chemicals.Herein,we contribute a robust metal-organic cage(MOC),denoted as TCPB-1,comprising a bulky Lewis acid functionalized linker,which can in situ form frustrated Lewis pairs(FLPs)upon the addition of Lewis basic substrates to efficiently drive CO_(2)transformation.Significantly,the incorporation of Lewis acidic boron sites within TCPB-1 promotes the efficient CO_(2)conversion to potentially medicinal benzimidazole derivatives via an FLPmediated pathway,and boosts the stability/durability of the FLP catalyst.In addition,the underlying catalysis mechanism has been established by combined experimental and molecular simulation studies.This work not only advances FLP/MOC as a new type of highly efficient catalyst for CO_(2)chemical fixation,but also opens a new avenue to design heterogeneous FLP-based catalysts for small molecule activation and beyond.

Photochemical and Electrochemical Carbon Dioxide Utilization with Organic Compounds

In the last few years, photochemical and electrochemical CO2 transformations have attracted increasing attention in response to topical interest in renewable energy and green chemistry. The present minireview offers an overview about the current approaches for the photochemical and electrochemical carbon dioxide fixation with organic compounds. Valuable products, including carboxylic acids and heterocyclic compounds, are accessible through carboxylation and carboxylative cyclization, respectively. In photochemical and electrochemical processes, photo- or electro-induced radical ions or other high-energy organic compounds are considered as key intermediates to react with CO2. Besides, activation of CO2 to produce radical anion has also been reported.

CO_(2) capture and utilization with solid waste

Nowadays,the massive consumption of fossil fuels and the resulting excessive emission of carbon dioxide(CO_(2))have broken the original carbon balance of nature,resulting in global warming and the consequent detrimental environmental impacts.To address these issues,various initiatives have been proposed,among which CO_(2) cap-ture and utilization(CCU)is considered as the direct way to mitigate the accumulation of CO_(2) in the atmosphere.Although a plethora of CO_(2) capture reagents and utilization routes have been developed,the cost of CO_(2) capture reagents as well as the amount of CO_(2) utilization still encounters limitations.Recently,CCU with solid wastes have attracted sustained attention due to its ability to synchronize CO_(2) fixation with solid wastes utilization.Especially,the huge amount and low cost of the solid wastes can promote the economic fixation of CO_(2) and thus contribute significantly to the carbon sink.Given the tremendous utility of this strategy,this review article summarizes the state-of-the-art of CO_(2) capture and utilization with solid wastes such as steel slag,concrete waste,fly ash,red mud,calcium carbide residue,and biomass etc.And three parts including CO_(2) mineralization,solid waste-based catalyst promoted CO_(2) transformation,and collaborative transformation of CO_(2) and solid waste are introduced according to the roles of solid waste in CO_(2) utilization.We hope this review can arouse broad concern and spur further development in this field.

Mesoporous zeolites for biofuel upgrading and glycerol conversion

With the recent emphasis and development of sustainable chemistry, the conversion of biomass feed- stocks into alternative fuels and fine chemicals over various heterogeneous catalysts has received much attention. In particular, owing to their uniform micropores, strong acidity, and stable and rigid frameworks, zeolites as catalysts or co-catalysts have exhibited excellent catalytic performances in many reactions, including hydrodesulfurization, Fischer-Tropsch synthesis, and hydrodeoxygenation. However, the relatively small sizes of the zeolite micropores strongly limit the conversion of bulky biomolecules. To overcome this issue, mesoporous zeolites with pores larger than those of biomolecules have been synthesized. As expected, these mesoporous zeolites have outperformed conventional zeolites with improved activ- ities, better selectivities, and longer catalyst lives for the upgrading of pyrolysis oils, the transformation of lipids into biofuels, and the conversion of glycerol into acrolein and aromatic compounds. This review briefly summarizes recent works on the rational synthesis of mesoporous zeolites and their superior catalytic properties in biomass conversion.

Toward Rational Design of Carbon Nanodots with High Photothermal Efficiency for Tumor Photothermal Therapy

Comprehensive Summary Carbon nanodots(CDs)with high photothermal performance are ideal candidates for tumor photothermal therapy(PTT).Herein,we investigated the photothermal performance of CDs synthesized from urea and citric acid via solvothermal method in dimethyl sulfoxide(DMSO)at different temperatures.Photothermal conversion efficiency(PCE)of up to 61.3%was obtained in the CDs synthesized at 150℃(150-CDs),which is much better than the CDs synthesized at 180℃(180-CDs).By analyzing the morphologies,chemical structures,and absorption spectra of these CDs,we found that the photothermal effect of the CDs was due to the lattice vibration of their carbonized cores.

MOFs in Emerging Solar Cells

Metal-organic framework(MOF)materials have attracted intense scientific interest in the solar cell research community owing to their unique physiochemical properties and various preparation methods.The photovoltaic performance and stability of resultant optoelectronic devices can also be improved by adopting MOF materials.This review pays close attention to the summary and generalization of recent representative achievements in solar cells by utilizing MOFs,including dye-sensitized solar cells,perovskite solar cells,organic solar cells,and so on.

Highly Conductive Poly(Imide–Imine)Hybrid Vitrimer-Graphene Aerogel Composites

Comprehensive Summary,Although polyimides(PIs)have shown great potential for a broad range of applications,it remains very challenging to achieve the malleability,rehealability and recyclability for PIs and their composites targeting various applications,particularly for the rapidly emerging flexible and stretchable electronics.Herein,malleable conductive poly(imide-imine)hybrid(PIIH)vitrimer-graphene aerogel(GA)composites have been prepared,for the first time,via simple sol-gel film formation followed by heat-press.The resulting PIIH-GA composites exhibit not only the highly desired properties of thermosetting(strong mechanical strength)and thermoplastic(reprocessability)polymers,but also good conductivity enabled by the GA filler.PIIH3-GA-10(with 10 wt%GA)showed one of the highest electrical conductivities(26.7 S/m)for PI-based composites,as well as good electromagnetic interference(EMI)shielding performance.Moreover,the PIIH-GA films could maintain good performance during stretching and even after chemical recycling,which opens new opportunities for flexible and sustainable electronics development.

Carbon Nitride with Single-Atom Nickel as Co-Catalyst for Visible-Light Promoted C—O Coupling

Solar-driven cross-coupling reactions by dual nickel/photocatalysis under mild conditions have received considerable attention.However,the existing photo/nickel dual catalytic cross-coupling reactions require the addition of expensive photosensitizers and organic ligands,and the catalytic activity is inadequate.Herein,we report a nickel single-atom heterogeneous catalyst supported on mesoporous carbon nitride for photocatalytic C—O coupling reaction between 4-bromobenzonitrile and ethanol,affording 4-ethoxybenzonitrile in excellent yield compared to a semi-heterogeneous catalytic system.The catalytic system exhibits a broad substrate scope including ketones,aldehydes,esters,and amides.This work presents a simple and cost-effective strategy for anchoring metal single atoms onto carbon nitride,providing a new platform for enabling high-performance photocatalytic production of aryl ether compounds.

Iron-catalyzed selective oxidation of 5-hydroxylmethylfurfural in air:A facile synthesis of 2,5-diformylfuran at room temperature

An iron（Ⅲ）-catalyzed selective oxidation of 5-HMF to 2,5-DFF in air at room temperature was developed.This approach gives 2,5-DFF with good selectivity and yields. Additionally, a two-step process was developed for the oxidation of 2,5-DFF to 2,5-FDCA at remarkably high substrate concentrations. This work demonstrates unequivocally the great potential of iron as a cheap and earth-abundant catalyst for the development of new protocols for the conversion of biomass to value-added chemicals.