Approaches to Improving Selectivity During Photoelectrochemical Transformation of Small Molecules

Photoelectrochemical (PEC) small-molecule oxidation can selectively transform substrates into high-value-added fine chemicals and increase the rate of cathode hydrogen evolution. Nevertheless, achieving high-selectivity PEC oxidation of small molecules to produce specific products is a very challenging task. In general, selectivity can be improved by changing the surface catalyticsites of the photoanode and modulating the interfacial environments of the reactions. Herein, recent advances in approaches to improving selective PEC oxidation of small molecules are introduced. We first briefly discuss the basic concept and fundamentals of small-molecule PEC oxidation. The reported approaches to improving the performance of selective PEC oxidation of small molecules are highlighted from two aspects: (1) changing the surface properties of photoanodes by selecting suitable materials or modifying the photoanodes and (2) mediating the oxidation reactions using redox mediators. The PEC oxidation mechanism of these studies is emphasized. We also discuss the challenges in this research direction and offer a perspective on the further development of selective PEC-based small-molecule transformation.

Alkyl chain modulation of asymmetric hexacyclic fused acceptor synergistically with wide bandgap third component for high efficiency ternary organic solar cells

Herein,two asymmetric hexacyclic fused small molecule acceptors(SMAs),namely BP4F-HU and BP4F-UU,were synthesized.The elongated outside chains in the BP4F-UU molecule played a crucial role in optimizing the morphology of blend film,thereby improving charge mobility and reducing energy loss within the corresponding film.Notably,the PM6:BP4F-UU device exhibited a higher open-circuit voltage(V_(oc))of 0.878 V compared to the PM6:BP4F-HU device with a V_(oc)of 0.863 V.Further,a new wide bandgap SMA named BTP-TA was designed and synthesized as the third component to the PM6:BP4F-UU host binary devices,which showed an ideal complementary absorption spectrum in PM6:BP4F-UU system.In addition,BTP-TA can achieve efficient intermolecular energy transfer to BP4F-UU by fluorescence resonance energy transfer(FRET)pathway,due to the good overlap between the photoluminescence(PL)spectrum of BTP-TA and the absorption region of BP4F-UU.Consequently,ternary devices with 15wt%BTP-TA exhibits broader photon utilization,optimal blend morphology,and reduced charge recombination compared to the corresponding binary devices.Consequently,PM6:BP4F-UU:BTP-TA ternary device achieved an optimal power conversion efficiency(PCE)of 17.83%with simultaneously increased V_(oc)of 0.905 V,short-circuit current density(J_(sc))of 26.14 mA/cm^(2),and fill factor(FF)of 75.38%.

Review on Chemical Stability of Lead Halide Perovskite Solar Cells

Lead halide perovskite solar cells(PSCs) have become a promising next-generation photovoltaic technology due to their skyrocketed power conversion efficiency. However, the device stability issues may restrict their commercial applications, which are dominated by various chemical reactions of perovskite layers. Hence, a comprehensive illustration on the stability of perovskite films in PSCs is urgently needed. In this review article, chemical reactions of perovskite films under different environmental conditions(e.g., moisture,oxygen, light) and with charge transfer materials and metal electrodes are systematically elucidated. Effective strategies for suppressing the degradation reactions of perovskites, such as buffer layer introduction and additives engineering,are specified. Finally, conclusions and outlooks for this field are proposed. The comprehensive review will provide a guideline on the material engineering and device design for PSCs.

Engineering Spin States of Isolated Copper Species in a Metal-Organic Framework Improves Urea Electrosynthesis

The catalytic activities are generally believed to be relevant to the electronic states of their active center, but understanding this relationship is usually difficult. Here, we design two types of catalysts for electrocatalytic urea via a coordination strategy in a metal–organic frameworks: Cu^(Ⅲ)-HHTP and Cu^(Ⅱ)-HHTP. Cu^(Ⅲ)-HHTP exhibits an improved urea production rate of 7.78 mmol h^(−1)g^(−1) and an enhanced Faradaic efficiency of 23.09% at-0.6 V vs. reversible hydrogen electrode, in sharp contrast to Cu^(Ⅱ)-HHTP.Isolated CuⅢspecies with S = 0 spin ground state are demonstrated as the active center in Cu^(Ⅲ)-HHTP, different from Cu^(Ⅱ) with S = 1/2 in Cu^(Ⅱ)-HHTP. We further demonstrate that isolated Cu^(Ⅲ)with an empty dx2-y20orbital in Cu^(Ⅲ)-HHTP experiences a single-electron migration path with a lower energy barrier in the C–N coupling process, while Cu^(Ⅱ)with a single-spin state( d_(x2-y2)^(1)) in Cu^(Ⅱ)-HHTP undergoes a two-electron migration pathway.

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.

Eco-friendly aqueous foam stabilized by cellulose microfibers with great salt tolerance and high temperature resistance

A low-cost eco-friendly aqueous foam,especially the robust foam with great tolerance to high salinity and high temperature,is in great demand in the oil industry,e.g.,oil and gas well or geothermal well drilling.Herein,an ultra-stable aqueous foam was developed using the biodegradable cellulose microfiber(CMF)as a foam stabilizer.The foam stabilized by CMF shows excellent tolerance to the high concentration of NaCl(6.0 wt%)and CaCl_(2)(0.25 wt%)and the related drainage half-life times(T_(0.5))reach 1750 and 2340 s respectively.By contrast,the foams without CMF are completely drained(T_(0.5)=0 s)when NaCl concentration is greater than 6.0 wt%or CaCl_(2) concentration is greater than 0.20 wt%.Notably,T0.5 of the foams stabilized by CMF at these saline concentrations still can maintain above 1000 s even after aging at 120℃ for 16 h,exhibiting an outstanding foam-stabilizing performance at high temperature.Experimental results suggest that the salt and high-temperature tolerance of CMF in foam stabilization is attributed to the electrically uncharged surfaces,the formation of a gel-like structure and the excellent thermal stability.This work not only provides a promising candidate of aqueous foam stabilizer to deal with high temperature and high salinity but also presents a natural-based solution for an environmentally friendly drilling industry in the future.

Quantum Dynamics Calculations on Isotope Effects of Hydrogen Transfer Isomerization in Formic Acid Dimer

We present a quantum dynamics study on the isotope effects of hydro-gen transfer isomerization in the formic acid dimer,and this is achieved by multidimensional dy-namics calculations with an efficient quantum mechanical theoretical scheme developed by our group,on a full-dimensional neural network ab initio potential energy surface.The ground-state and fundamental tun-neling splittings for four deuterium isotopologues of formic acid dimer are considered,and the calculated results are in very good general agreement with the avail-able experimental measurements.Strong isotope effects are revealed,the mode-specific funda-mental excitation effects on the tunneling rate are evidently influenced by the deuterium sub-stitution of H atom with the substitution on the OH bond being more effective than on the CH bond.Our studies are helpful for acquiring a better understanding of isotope effects in the double-hydrogen transfer processes.

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.

Pushing the Electrochemical Performance Limits of Polypyrrole Toward Stable Microelectronic Devices

Conducting polymers have achieved remarkable attentions owing to their exclusive characteristics,for instance,electrical conductivity,high ionic conductivity,visual transparency,and mechanical tractability.Surface and nanostructure engineering of conjugated conducting polymers offers an exceptional pathway to facilitate their implementation in a variety of scientific claims,comprising energy storage and production devices,flexible and wearable optoelectronic devices.A two-step tactic to assemble high-performance polypyrrole(PPy)-based microsupercapacitor(MSC)is utilized by transforming the current collectors to suppress structural pulverization and increase the adhesion of PPy,and then electrochemical co-deposition of PPy-CNT nanostructures on rGO@Au current collectors is performed.The resulting fine patterned MSC conveyed a high areal capacitance of 65.9 mF cm^(−2)(at a current density of 0.1 mA cm^(−2)),an exceptional cycling performance of retaining 79%capacitance after 10,000 charge/discharge cycles at 5 mA cm^(−2).Benefiting from the intermediate graphene,current collector free PPy-CNT@rGO flexible MSC is produced by a facile transfer method on a flexible substrate,which delivered an areal capacitance of 70.25 mF cm^(−2) at 0.1 mA cm^(−2) and retained 46%of the initial capacitance at a current density of 1.0 mA cm^(−2).The flexible MSC is utilized as a skin compatible capacitive micro-strain sensor with excellent electromechanochemical characteristics.

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.

Selectively reductive amination of levulinic acid with aryl amines to N-substituted aryl pyrroles

Synthesizing nitrogen(N)-containing molecules from biomass derivatives is a new strategy for production of this kind of chemicals.Herein,for the first time we present the synthesis of N-substituted aryl pyrroles via reductive amination/cyclization of levulinic acid(LA)with primary aromatic amines and hydrosilanes(e.g.,PMHS)over Cs F,and a series of N-substituted aryl pyrroles could be obtained in good to excellent yields at 120○C.The mechanism investigation indicates that the reaction proceeds in two steps:the cyclization between amine and LA occurs first to form intermediate 5-methyl-N-alkyl-1,3-dihydro-2H-pyrrolones and their isomeride(B),and then the chemo-and region-selective reduction of intermediates take place to produce the final products.This approach for synthesis of N-substituted aryl pyrroles can be performed under mild and green conditions,which may have promising applications.

Charging Mechanism of Lightning at the Molecular Level

Cloud electrification is one of the oldest unresolved puzzles in the atmospheric sciences. Though many mechanisms for charge separation in clouds have been proposed, a quantitative understanding of their respective contribution in a given meteorological situation is lacking. Here we suggest and analyze a hitherto little discussed process. A qualitative picture at the molecular level of the charge separation mechanism of lightning in a thundercloud is proposed. It is based on two key physical/chemical natural phenomena, namely, internal charge separation of the atmospheric impurities/aerosols inside an atmospheric water cluster/droplet/ice particle and the existence of liquid water layers on rimers (graupels and hailstones) forming a layer of dipoles with H+ pointing out from the air-water interface. Charge separation is achieved through strong collisions among ice particles and water droplets with the rimers in the turbulence of the thundercloud. This work would have significant contribution to cloud electrification and lightning formation.

Synthesis and Photochemistry of Diphenylchlorin and Diphenylbacteriochlorin

Diphenylchlorin (DPC) and diphenylbacteriochlorin (DPBC) were synthesized for the first time from reduction of 5,10-diphenylporphyrin (DPP). As photosensitizers they have sizable absorption in the red region of the visible spectrum. The high yield of DPC.-photosensitized generation Of O-1(2), and the EPR studies in homogenerous solution showed that the photodynamic action of DPP-based photosensitizers may proceed via type I and type II machanisms.

Stereochemistry Control in Direct 1α-Hydroxylation of 5,6-trans-Vitamin D_(3) by Solid Support

A solid-phase synthesis of 1α-hydroxylation of 5,6-trans-vitamin D3 8 is described.The solid phase resin acts as a special protecting group, which gives a higher stereoselectivity in oxidation step than classical protecting groups. The stereochemistry control is favored by using high crosslinkage polymer support in a poor solvent. This work may be of benefit to the synthesis of vitamin D system.

Sixty Years of Chemistry at CAS

As one of the fundamental and key disciplines of natural sciences, chemistry deals with the properties, composition, structure, transformation and applications of substances.It could be further divided into several branches, such as inorganic chemistry, organic chemistry, physical chemistry, polymer chemistry, analytical chemistry and chemical engineering.In recent years, many new branches and fields have emerged amide the continuous development of chemistry and its interdisciplinary research with mathematics, physics, astronomy, earth science, biology, medical science, materials science, and environmental science.

Celebrating the 60th Anniversary of Institute of Chemistry,Chinese Academy of Sciences

Institute of Chemistry,Chinese Academy of Sciences(ICCAS)was established in 1956.ICCAS is a multidisciplinary research institute dedicated to the basic research in broad fields of chemical sciences,and to the key development of the innovative high-technology aiming at the imperative national needs and important strategic targets,as well as to the collaborative high-technology applications and transfers.With the development of 60 years,ICCAS has become one of the leading chemistry institutions in China with high international visibility.

A special column highlighting young scientists at Institute of Chemistry, Chinese Academy of Sciences (ICCAS)

Just seeing off the BOth anniversary of the Institute of Chemistry, Chinese Academy of Sciences （ICCAS）, we are here with pleasure to conduct A Special Column for Young Scientists at ICCAS published in Chinese Chemistry Letters （CCL） endeavoring to disseminate positive energy of several enthusiastic chemists and spread their recent research to the global scientific community.

Properties of Functionalized Graphene/Room Temperature Vulcanized Silicone Rubber Composites Prepared by an In-situ Reduction Method

Functionalized graphene oxide （FGO） was prepared by treating graphene oxide with y-aminopropyl triethoxysilane （KH-550） before the mixture was dispersed into a, ω-dihydroxy polydimethylsiloxane to get room temperature vulcanized （RTV） silicone rubber composites by solution casting. The cured composites were then reduced with hydrazine hydrate to obtain functionalized graphene （FG）/RTV silicone rubber composites. The structures of FGO and the resultant composites were characterized by atomic force microscopy, FT-IR spectra and X-ray diffraction. KH-550 was found to be grafted onto graphene sheets, leading to an increased interlayer spacing. Significant improvements in thermal and mechanical properties were obtained. Both the FGO/RTV silicone rubber composite contain 1.0 wt% of FGO, and its reduced product showed an increase of one-step weight loss temperature with 61 ℃ and 133 ℃ higher than that of pure silicone rubber. Tensile strength and elongation at break of FG/RTV silicone rubber composite （with 0.5 wt% FGO content） increased by 175% and 67%, respectively, compared with those of pure silicone rubber.

Homogeneous Acetylation of Cellulose at Relatively High Concentrations in an Ionic Liquid

At relatively high cellulose mass concentrations(8%,10%,and 12%),homogeneous acetylation of cellulose was carried out in an ionic liquid,1-allyl-3-methylimidazolium chloride(AmimCl).Without using any catalyst,cellulose acetates(CAs)with the degree of substitution(DS)in a range from 0.4 to 3.0 were synthesized in one-step.The effects of reaction time,temperature and molar ratio of acetic anhydride/anhydroglucose unit(AGU) in cellulose on DS value of CAs were investigated.The synthesized CAs were characterized by means of FT-IR, NMR,and solubility,mechanical and thermal tests.After the acetylation,the used ionic liquid AmimCl was easily recycled and reused.This study shows the potential of the homogeneous acetylation of cellulose at relatively high concentrations in ionic liquids in future industrial applications.

POLYMERIZATION OF OCTAMETHYLCYCLOTETRASILOXANE WITH HEXAMETHYLDISILAZYL-LITHIUM AS INITIATOR

This work focused on the anionic polymerization of octamethylcyclotetrasiloxane (D-4, D = Me2SiO2/2) initiated by a new kind of initiator hexamethydisilazyl-lithium (MMNLi). Si-29-NMR spectroscopy and gas chromatography (GC) were used to characterize the polymerization products. The process was accelerated by adding a small amount of high activity monomer D-3 and by raising the polymerization temperature. At the end of polymerization more than 95% of the monomer was converted to polymer and only a very small amount of D-4 and D-5 remained in the polymers.