Recent advances in metal-free catalysts for the synthesis of cyclic carbonates from CO_2 and epoxides

The aim of ＂green chemistry＂ and ＂atom economy＂ is to utilize carbon dioxide and replace harmful reactants such as CO and phosgene for the production of cyclic carbonates. In this paper, metal-free catalysts including organic bases, ionic liquids, supported catalysts, organic copolymers and carbon materials for the synthesis of cyclic carbonates by the cycloaddition of carbon dioxide to epoxides are reviewed. Recent advances in the design of the catalysts and the understanding of the reaction mechanism are summarized and discussed. The synergistic effects of organic bases and hydrogen bond donors, organic bases and nucleophilic anions, hydrogen bond donors and nucleophilic anions and active components and supports are highlighted. The challenge is to develop metal-free catalysts suitable for carbon dioxide capture and fixation. The ultimate goal is to synthesize cyclic carbonates in a flow reactor directly using carbon dioxide from industrial flue gas at ambient temperature and atmospheric pressure. By using synergetic effects, a multi-functional approach can meet the design strategy of metal-free catalysts for carbon dioxide adsorption and activation as well as epoxide ring opening.

Synthesis of cyclic carbonates from epoxides or olefins and CO_2 catalyzed by metal-organic frameworks and quaternary ammonium salts

Catalytic properties of the metal-organic framework Cr-MIL-101 in solvent-free cycloaddition of CO2 to epoxides to produce cyclic carbon- ates using tetrabutylammonium bromide as co-catalyst have been explored under mild reaction conditions （8 bar CO2, 25 ~C）. Styrene and propylene carbonates were formed with high yields （95% and 82%, respectively）. Catalytic performance of Cr-MIL-101 was compared with other MOFs： Fe-MIL-101, Zn-MOF-5 and HKUST-1, The catalytic properties of different quaternary ammonium bromides, Cr-MIL-101 as well as PW12/Cr-MIL-101 composite material have been assessed in oxidative carboxylation of styrene in the presence of both tert-butyl hydroperoxide and H202 as oxidants at 8-100bar CO2 and 25-80 ~C with selectivity to styrene carbonate up to 44% at 57% substrate conversion.

Synthesis of Cyclic Carbonates from CO_2 and Epoxides Catalyzed by Hexaalkylguanidinium Halides

Hexaalkylguanidinium halides exhibit an efficient catalytic activity in the synthesis of cyclic carbonates from epoxides and carbon dioxide. By this method cyclic carbonates can be obtained in a high yield and a high selectivity at a low temperature and atmospheric pressure. This procedure is easy for the product isolation and recycling of the catalyst.

Preparation of Ionic Liquids Immobilized on FMIL-101 Catalysts for Conversion of CO_(2)to Propylene Carbonate

Metal-organic frameworks(MOFs)have attracted considerable research attention as a new type of porous material for catalytic applications.Herein,2,5-dihydroxyterephthalic acid was proposed to replace conventional terephthalic acid and reacted with chromic nitrate nonahydrate to synthesize a functional metal–organic framework(FMIL-101).This was then used to immobilize various compound ionic liquids to prepare three ionic liquids immobilized on FMIL-101 catalysts,namely,FMIL-101-[HeMIM]Cl/(ZnBr_(2))_(2),FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),and FMIL-101-[AeMIM]Br/(ZnBr_(2))_(2).After characterization by Fourier-transform infrared spectroscopy,X-ray diffraction,ultraviolet spectroscopy,thermogravimetry,specific surface area analysis,and scanning electron microscopy,the catalysts were used to mediate cycloaddition reactions between carbon dioxide(CO_(2))and propylene oxide.The effects of reaction temperature,reaction pressure,reaction time,and catalyst dosage on the catalytic performance were investigated.The results revealed that the FMIL-101-supported CIL catalysts afforded the target product propylene carbonate with good catalytic performance and thermal stability.The optimal catalyst,FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),displayed a propylene oxide conversion of 98.64%and a propylene carbonate selectivity of 96.63%at a reaction temperature of 110℃,a reaction pressure of 2.0 MPa,a catalyst dosage of 2.0%relative to propylene oxide,and a reaction time of 2.5 h.In addition,the conversion and selectivity of the catalyst decreased slightly after four cycles.Additionally,the catalyst decreased slightly in catalytic performance after being recycled four times.

Efficient homogenous catalysis of CO_(2) to generate cyclic carbonates by heterogenous and recyclable polypyrazoles

The cycloaddition between CO_(2)and epoxides to produce cyclic carbonate is an attractive and efficiency pathway for the utilization of CO_(2)as C1 source.The development of catalyst to mediate cycloaddition between CO_(2)and epoxides at low temperature and pressure is still a challenge.Herein,a series of polypyrazoles with glass transition temperature(T_(g))in the range of 42.3-52.5℃ were synthesized and served as catalyst to mediate the cycloaddition of CO_(2)and epoxides by the assistant of tetrabutylammonium bromide.The catalytic behaviors of polypyrazole on the model cycloaddition of CO_(2)to epichlorohydrin,including the reaction parameters optimization and versatility were investigated in detail,and excellent yield(99.9%)and selectivity(99%)were obtained under the optimized reaction conditions of70℃ and 1.0 MPa for 6.0 h.Noteworthily,the polypyrazole acts as homogeneous catalyst during reaction(higher than T_(g)).And under room temperature,polypyrazoles can be easily separated and recovered,which is a promising feature of a heterogeneous catalyst.Furthermore,the reaction mechanism was proposed.The DFT calculation suggested that the formation of hydrogen bond between pyrazole and epoxide greatly reduced the energy barrier,which play an important role in promoting CO_(2)cycloaddition.

Immobilization of Glucoamylase onto Novel Porous Supports Containing Cyclic Carbonate

Glucoamylase was immobilized onto novel porous polymer supports containing cyclic carbonate. The relationship between activity of immobilized glucoamylase and the properties of porous polymer supports was investigated. The operation stability and storage stability of immobilized glucoamylase were studied.

Chemical fixation of carbon dioxide to cyclic carbonates catalyzed by zinc(Ⅱ) complex bearing 1,2-disubstituted benzimidazole ligand

A new zinc(II)complex of formula[ZnCl2(L1)2](1)[L1=2‐(2‐thienyl)‐1‐(2‐thienylmethyl)‐1Hbenzimidazole]was synthesized and fully characterized by nuclear magnetic resonance and infrared spectroscopy,elemental analysis,electrospray ionization high‐resolution mass spectrometry,and thermogravimetric analysis.The molecular structure was confirmed by single‐crystal X‐ray diffraction.Complex1consists of mononuclear tetrahedral zinc(II)units with a locked geometry resulting from weak intramolecular S···?and?–?interligand interactions.The benzimidazole ligand and its zinc(II)complex were readily obtained through a simple synthetic route.The catalytic activity of1was investigated in the coupling of carbon dioxide with epoxides to produce cyclic carbonates,and a series of parameters were evaluated.The complex efficiently catalyzed the transformation of various epoxides under solvent‐free conditions,with good conversions,turnover numbers,and turnover frequencies.

Using cyclic alternating water injection to enhance oil recovery for carbonate reservoirs developed by linear horizontal well pattern

In view of high water cut and low oil recovery caused by the unidirectional flow in linear pattern of horizontal wells for the carbonate reservoirs in the Middle East,this paper provides a novel approach to improve oil recovery by converting linear water injection to cyclic alternating water injection patterns including cyclic alternating water injection with apparent inverted seven-spot pattern or apparent five-spot pattern and cyclic differential alternating water injection.The main advantage of using this strategy is that the swept efficiency is improved by changing injection-production streamlines and displacement directions,which means displacement from two different direction for the same region during a complete cycle.This technology is effective in increasing the swept efficiency and tapping the remaining oil,thus resulting in higher oil recovery.Field application with three new patterns in a carbonate reservoir in the Middle East is successful.By optimizing injection and production parameters based on the cyclic alternating well pattern,the test well group had a maximum increase of daily oil production per well of 23.84 m^(3) and maximum water cut drop of 18%.By further optimizing the distance(keep a long distance)between the heels of injection and production wells,the waterflooding performance could be better with water cut decreasing and oil production increasing.

An Optimal Model for Carbon Sinks of CDM Project to Build a New Countryside Based on Cyclic Economy under Uncertainty

Based on the status and characteristics of Clean Development Mechanism （CDM） renewable energy project and the mode of cyclic economy, aimed at achieving the maximum capacity of carbon sinks in the system, Lvjin Jiayuan—New Countryside Distripark CDM project in Wuchuan County was taken as an example for developing an interval linear programming （ILP） model to optimize the crops planting scheme and cows breeding scheme by using interval optimal method. The case showed that the optimized crops planting scheme and cows breeding scheme obtained from the optimal model was reasonable with relatively preferable overall performance. In the context of meeting economic benefits and fertilizer, electricity demand, [231 287.8, 273 312.7] t of CO2 could be absorbed and fixed, which had increased by [12.94, 33.46]% compared with the feasibility scheme of case project and provided technical support for making the decision in CDM project.

Research on the Low-carbon-high-value Agriculture Technology in the Comprehensive Improvement of Intra-county Environment Pollution——Taking the Development of Cultivation and Breeding Industry in the Ecological Cyclic Agricultural Garden in Shaoshan Irri

The comprehensive improvement strategy of intra-county environment pollution in the city and countryside was searched.By the research method which combined the microscopic view,the macroscopic view with the dynamic perspective,the seriousness of rural water quality,soil and atmospheric pollution in Xiangxiang,Xiangtan and the surrounding areas in Shaoshan irrigated area was revealed.The control measure which was 'four-dimensional pollution in the city and countryside'—— low-carbon-high-value agriculture and the technology innovation was proposed.The low-carbon-high-value technology innovation industrialization demonstration in three parts which included the pre-production,mid-production and post-production deep-processing of cultivation and breeding industry in the ecological cyclic agricultural garden in Shaoshan irrigated area was the driving force.We tried to propel the low-carbon ecological cultivation and breeding industry which included the paddy rice,grass,tree,medicinal herbs and pig,cow,chick,duck,fish.We wanted to relieve the structural unbalance of previous cultivation and breeding industry,'cheap grain hurting the farmers' and the short-leg problem of social-economic-ecological benefit.The results showed that the low-carbon-high-value agricultural system was a poly-generation technology system which promoted the multi-level and grading utilization,saved the energy,reduced the consumption and cleaned the production based on the ecology.

Ru(II)-Catalyzed ortho C-H Allylation of N-Aryl-7-azaindoles with 2-Methylidene Cyclic Carbonate

A Ru(II)-catalyzed ortho allylation reaction of N-aryl-7-azaindole with readily available 2-methylidene cyclic carbonate has been developed.This reaction is an effective pathway for synthesizing 7-azaindole derivatives with a wide scope of substrates and high yields.In addition,the method can be extended to the allylation of other heterocyclic compounds and several cyclic carbonates,highlighting the practicality of this strategy for synthesis.

INVESTIGATION OF FRACTURE DESIGN FOR MEDIUM CARBON STEEL UNDER EXTRA-LOW CYCLIC FATIGUE IN AXIAL LOADING

The extra-low cyclic fracture problem of medium carbon steel under axial fatigue loading was investigated. Several problems, such as the relations of the cycle times to the depth and tip radius of the notch, loading frequency, loading range and the parameters of fracture design for medium carbon steel on condition of extra-low axial fatigue loading were discussed based on the experiments. Experimental results indicated that the tension-pressure fatigue loading mode was suitable for extra-low cyclic fatigue fracture design of medium carbon steel and it resulted in low energy consumption, fracture surface with high quality, low cycle times, and high efficiency. The appropriate parameters were as follows： loading frequency 3-5 Hz, notch tip radius r = （0.2-0.3） mm, opening angle α = 60°, and notch depth t = （0.14-0.17）D.

Electrochemical preparation of the Fe-Ni36 Invar alloy from a mixed oxides precursor in molten carbonates

The Fe-Ni36 alloy was prepared via the one-step electrolysis of a mixed oxides precursor in a molten Na2CO3-K2CO3 eutectic melt at 750℃,where porous Fe_(2)O_(3)-NiO pellets served as the cathode and the Ni10 Cu11 Fe alloy was an inert anode.During the electrolysis,Ni O was preferentially electro-reduced to Ni,then Fe_(2)O_(3)was reduced and simultaneously alloyed with nickel to form the Fe-Ni36 alloy.Different cell voltages were applied to optimize the electrolytic conditions,and a relatively low energy consumption of 2.48 k W·h·kg^(-1) for production of Fe Ni36 alloy was achieved under 1.9 V with a high current efficiency of 94.6%.The particle size of the alloy was found to be much smaller than that of the individual metal.This process provides a low-carbon technology for preparing the Fe-Ni36 alloy via molten carbonates electrolysis.

Efficient fixation of CO_(2) into propylene carbonate with [BMIM]Br in a continuous-flow microreaction system

Utilization of carbon dioxide(CO_(2)) is of great significance in the development of CO_(2) absorption and the solution of greenhouse gas effect.Highly efficient conversion of CO_(2) into cyclic carbonate with green catalysts is essential for the more sustainable expansion of CO_(2) fixation.Traditional batch reactor is limited by low efficiency, high cost and low security. Meanwhile, continuous flow system showcased a myriad of virtues, including shortening the residence time from hours to seconds, and decreasing reaction temperature, and possessing the nature of easy industrial scale-up. In this paper, a continuous-flow microreaction system was developed to synthesis propylene carbonate(PC) from propylene oxide(PO) and CO_(2) using 1-butyl-3-methylimidazolium bromide([BMIM]Br) as catalyst. By observing the flow patterns inside microreaction system, the effects of reaction temperature, molar fraction of catalyst, operating pressure, residence time, molar ratio of CO_(2)/PO as well as recycling performance of catalyst on the overall performances were comprehensively evaluated into details. Under different reaction conditions,the flow patterns were set to vary between slug flow and annular flow. The results showed that the yield of propylene carbonate(PC) can reach99.7% at 140℃ and 3.0 MPa with the residence time of 166 s, while the recycling performance of the designed system greatly conforms the future trend of green chemistry.

Cyclic Voltammetry Determination of Epinephrine with a Nano-gold Modified Glassy Carbon Electrode in the Presence of High Concentration Ascorbic Acid

Nano-gold (NG) modified glassy carbon electrodes (GCEs) were used for determination of epinephrine (EP) in the presence of high concentration ascorbic acid (AA) by cyclic voltammetry (CV). This modified electrode can not only catalytically oxidize EP and AA, but also separate the catalytic peak potentials of EP and AA by about 183.5 mV. In pH = 7.0 ogisogate byffer solution, the linear range of epinephrine was 5 106 ~ 1 ?10-4 mol/L.

Effect of Initial Principal Stress Direction on the Dynamic Characteristics of Carbonate Sand

The dynamic characteristics of carbonate sand under wave loads are very important for constructions on the ocean floor. The initial principal stress direction has been known to exert some influence on the dynamic characteristics of sand during cyclic loading. In an effort to investigate this aspect of the problem, several series of cyclic undrained tests were carried out on a saturated and loose sample of carbonate sand using a geotechnical static and dynamic universal triaxial shear apparatus. In this test apparatus, a hollow cylindrical sand specimen is subjected to a simultaneous application of both triaxial and torsional modes of shear stresses, which brings about the continuous rotation of principal stress axes. The test results indicated that the initial principal stress direction has a considerable influence on the dy- namic strength of loose carbonate sand and with the increase of initial orientation of principal stress, dynamic strength will be reduced, the cyclic pore pressure increased, but the residual pore pressure reduced.

Experimental investigation of changes in petrophysical properties and structural deformation of carbonate reservoirs

To examine the effect of pressure on pore structure and petrophysical properties of carbonate rock, the porosity, permeability, CT scanning, SEM and elastic wave velocity of two carbonate core plug samples from an oilfield in Southwest Iran were analyzed under cyclic pressure. One of the plugs was calcite and the other was dolomite with anhydrite nodules. The cyclic pressure exerted on the samples increased from 13.79 MPa to 27.58 MPa in six steps, and the variations in petrophysical properties of the two samples at different pressure loading and unloading steps were counted and analyzed. The results show that the calcite sample decreases in porosity and permeability with the increase of pressure, which is consistent with the results from compression and shear wave velocity tests. In the dolomite sample, the decreasing trend was not observed;fluctuations of compressive and shear velocities were observed during the loading stage, which may be due to different geometries of the pores and the porosity variation in the sample. Understanding the variation of carbonate petrophysical properties with pressure is helpful for optimizing reservoir development scheme.

LiPF6 and lithium difluoro(oxalato)borate/ethylene carbonate+dimethyl carbonate+ethyl(methyl)carbonate electrolyte for LiNi0.5Mn1.5O4 cathode

LiODFB electrolyte’s compatibility with LiNi0.5Mn1.5O4high-voltage cathode material was studied by cyclic voltammetry, charge-discharge test and AC impedance. The results show that at 25 and 60 °C, the LiODFB-based electrolyte has better electrochemical stability than LiPF6. AC impedance plots show that the LiODFB battery has a lower charge-transfer resistance than LiPF6battery at 60 °C, which indicates that LiODFB battery has excellent cycling performance at high temperature. At 25 and 60 °C, the LiNi0.5Mn1.5O4/Li half cells with LiODFB or LiPF6as electrolyte all have simple redox peak, showing that each of them has an excellent reversibility. LiODFB battery has better cycle performance than LiPF6battery at 25 °C and 60 °C. At 25 °C, their 0.5C initial discharge specific capacities are 126.3 and 131.6 mA·h/g, and their capacity retention ratios of the 100th cycle are 97.1% and 94.7%, respectively. At 60 °C, their 0.5C initial discharge specific capacities are 132.6 and 129.1 mA·h/g, and their capacity retention ratios of the 100th cycle are 94.1% and 81.7%, respectively. © 2017, Central South University Press and Springer-Verlag GmbH Germany.

Accurate theoretical evaluation of strain energy of all-carboatomic ring(cyclo[2n]carbon),boron nitride ring,and cyclic polyacetylene

Cyclocarbon fully consists of sp-hybridized carbon atoms,which shows quite unusual electronic and geometric structures compared to common molecules.In this work,we systematically studied strain energy(SE)of cyclocarbons of different sizes using regression analysis method based on electronic energies evaluated at the very accurate DLPNO-CCSD(T)/ccp VTZ theoretical level.In addition,ring strain of two systems closely related to cyclocarbon,boron nitride(BN)ring,and cyclic polyacetylene(c-PA),is also explored.Very ideal relationships between SE and number of repeat units(n)are built for cyclo[2n]carbon,B_(n)N_(n),and[2n]c-PA as SE=555.0·n^(-1),145.1·n^(-1),and 629.8·n^(-1)kcal·mol^(-1),respectively,and the underlying reasons of the difference and similarity in their SEs are discussed from electronic structure perspective.In addition,force constant of harmonic potential of C-C-C angles in cyclocarbon is derived based on SE values,the result is found to be 56.23 kcal·mol^(-1)·rad^(-2).The possibility of constructing homodesmotic reactions to calculate SEs of cyclocarbons is also explored in this work,although this method is far less rigorous than the regression analysis method,its result is qualitatively correct and has the advantage of much lower computational cost.In addition,comparisons show thatωB97XD/def2-TZVP is a good inexpensive alternative to the DLPNO-CCSD(T)/cc-p VTZ for evaluating energies used in deriving SE,while the popular and very cheap B3LYP/6-31G(d)level should be used with caution for systems with global electron conjugation such as c-PA.