Structural Engineering of Anode Materials for Low-Temperature Lithium-Ion Batteries:Mechanisms,Strategies,and Prospects

The severe degradation of electrochemical performance for lithium-ion batteries(LIBs)at low temperatures poses a significant challenge to their practical applications.Consequently,extensive efforts have been contributed to explore novel anode materials with high electronic conductivity and rapid Li^(+)diffusion kinetics for achieving favorable low-temperature performance of LIBs.Herein,we try to review the recent reports on the synthesis and characterizations of low-temperature anode materials.First,we summarize the underlying mechanisms responsible for the performance degradation of anode materials at subzero temperatures.Second,detailed discussions concerning the key pathways(boosting electronic conductivity,enhancing Li^(+)diffusion kinetics,and inhibiting lithium dendrite)for improving the low-temperature performance of anode materials are presented.Third,several commonly used low-temperature anode materials are briefly introduced.Fourth,recent progress in the engineering of these low-temperature anode materials is summarized in terms of structural design,morphology control,surface&interface modifications,and multiphase materials.Finally,the challenges that remain to be solved in the field of low-temperature anode materials are discussed.This review was organized to offer valuable insights and guidance for next-generation LIBs with excellent low-temperature electrochemical performance.

Low-temperature characteristicsof rubbers and performance testsof type 120 emergencyvalve diaphragms

Purpose–The type 120 emergency valve is an essential braking component of railway freight trains,butcorresponding diaphragms consisting of natural rubber(NR)and chloroprene rubber(CR)exhibit insufficientaging resistance and low-temperature resistance,respectively.In order to develop type 120 emergency valverubber diaphragms with long-life and high-performance,low-temperatureresistant CR and NR were processed.Design/methodology/approach–The physical properties of the low-temperature-resistant CR and NRwere tested by low-temperature stretching,dynamic mechanical analysis,differential scanning calorimetryand thermogravimetric analysis.Single-valve and single-vehicle tests of type 120 emergency valves werecarried out for emergency diaphragms consisting of NR and CR.Findings–The low-temperature-resistant CR and NR exhibited excellent physical properties.The elasticityand low-temperature resistance of NR were superior to those of CR,whereas the mechanical properties of thetwo rubbers were similar in the temperature range of 0℃–150℃.The NR and CR emergency diaphragms metthe requirements of the single-valve test.In the low-temperature single-vehicle test,only the low-temperaturesensitivity test of the NR emergency diaphragm met the requirements.Originality/value–The innovation of this study is that it provides valuable data and experience for futuredevelopment of type 120 valve rubber diaphragms.

Boosting oxygen reduction activity and CO_(2) resistance on bismuth ferrite-based perovskite cathode for low-temperature solid oxide fuel cells below 600℃

Developing efficient and stable cathodes for low-temperature solid oxide fuel cells(LT-SOFCs) is of great importance for the practical commercialization.Herein,we propose a series of Sm-modified Bi_(0.7-x)Sm_xSr_(0.3)FeO_(3-δ) perovskites as highly-active catalysts for LT-SOFCs.Sm doping can significantly enhance the electrocata lytic activity and chemical stability of cathode.At 600℃,Bi_(0.675)Sm_(0.025)Sr_(0.3)FeO_(3-δ)(BSSF25) cathode has been found to be the optimum composition with a polarization resistance of 0.098 Ω cm^2,which is only around 22.8% of Bi_(0.7)Sr_(0.3)FeO_(3-δ)(BSF).A full cell utilizing BSSF25 displays an exceptional output density of 790 mW cm^(-2),which can operate continuously over100 h without obvious degradation.The remarkable electrochemical performance observed can be attributed to the improved O_(2) transport kinetics,superior surface oxygen adsorption capacity,as well as O_(2)p band centers in close proximity to the Fermi level.Moreover,larger average bonding energy(ABE) and the presence of highly acidic Bi,Sm,and Fe ions restrict the adsorption of CO_(2) on the cathode surface,resulting in excellent CO_(2) resistivity.This work provides valuable guidance for systematic design of efficient and durable catalysts for LT-SOFCs.

Advances in sodium-ion batteries at low-temperature: Challenges and strategies

With the continuing boost in the demand for energy storage,there is an increasing requirement for batteries to be capable of operation in extreme environmental conditions.Sodium-ion batteries(SIBs) have emerged as a highly promising energy storage solution due to their promising performance over a wide range of temperatures and the abundance of sodium resources in the earth's crust.Compared to lithiumion batteries(LIBs),although sodium ions possess a larger ionic radius,they are more easily desolvated than lithium ions.Fu rthermore,SIBs have a smaller Stokes radius than lithium ions,resulting in improved sodium-ion mobility in the electrolyte.Nevertheless,SIBs demonstrate a significant decrease in performance at low temperatures(LT),which constrains their operation in harsh weather conditions.Despite the increasing interest in SIBs,there is a notable scarcity of research focusing specifically on their mechanism under LT conditions.This review explores recent research that considers the thermal tolerance of SIBs from an inner chemistry process perspective,spanning a wide temperature spectrum(-70 to100℃),particularly at LT conditions.In addition,the enhancement of electrochemical performance in LT SIBs is based on improvements in reaction kinetics and cycling stability achieved through the utilization of effective electrode materials and electrolyte components.Furthermore,the safety concerns associated with SIBs are addressed and effective strategies are proposed for mitigating these issues.Finally,prospects conducted to extend the environmental frontiers of commercial SIBs are discussed mainly from three viewpoints including innovations in materials,development and research of relevant theoretical mechanisms,and intelligent safety management system establishment for larger-scale energy storage SIBs.

Temperature inversion enables superior stability for low-temperature Zn-ion batteries

It is challenging for aqueous Zn-ion batteries(ZIBs)to achieve comparable low-temperature(low-T)performance due to the easy-frozen electrolyte and severe Zn dendrites.Herein,an aqueous electrolyte with a low freezing point and high ionic conductivity is proposed.Combined with molecular dynamics simulation and multi-scale interface analysis(time of flight secondary ion mass spectrometry threedimensional mapping and in-situ electrochemical impedance spectroscopy method),the temperature independence of the V_(2)O_(5)cathode and Zn anode is observed to be opposite.Surprisingly,dominated by the solvent structure of the designed electrolyte at low temperatures,vanadium dissolution/shuttle is significantly inhibited,and the zinc dendrites caused by this electrochemical crosstalk are greatly relieved,thus showing an abnormal temperature inversion effect.Through the disclosure and improvement of the above phenomena,the designed Zn||V_(2)O_(5)full cell delivers superior low-T performance,maintaining almost 99%capacity retention after 9500 cycles(working more than 2500 h)at-20°C.This work proposes a kind of electrolyte suitable for low-T ZIBs and reveals the inverse temperature dependence of the Zn anode,which might offer a novel perspective for the investigation of low-T aqueous battery systems.

Efficient in-situ end-functionalization of polydienes by isothiocyanate via neodymium mediated coordinative chain transfer polymerization system

End-functionalization of polydiene rubbers can not only improve its compatibility with inorganic fillers,but also enhance the overall mechanical properties.Nevertheless,for traditional neodymium(Nd)diene polymerization systems,it is highly challenging to achieve such end-functionalizations,because most of polydienyl chains are capped withη3-allyl-Nd moiety during the end of polymerization,which shows very poor reactivity with nucleophile compounds.We launched a new diene polymerization strategy calling coordinative chain transfer polymerization(CCTP)[1].In such a system,all the polydienyl chains are capped withη1-allyl-Al moieties,which reveal greater reactivity with cyclic esters and epoxide compounds,providing an effective manner to prepare polydiene-polyester amphiphilic block copolymers.Inspired by such findings,we now show herein how such types of chain-ends react with isot-hiocyanate to demonstrate an efficient in-situ manner to access end-functionalized polydienes by using CCTP.

Nickel catalysts with asymmetric steric hindrance for ethylene polymerization

α-Diimide catalysts have attracted widespread attention due to their unique chain walking characteristics.A series ofα-diimide nickel/palladium catalysts with different electronic effects and steric hindrances were designed and synthesized for olefin polymerization.In this work,we synthesized a series of asymmetricα-diimide nickel complexes with different steric hindrances and used them for ethylene polymerization.These nickel catalysts have high ethylene polymerization activity,up to 6.51×10^(6)g·mol^(−1)·h^(−1),and the prepared polyethylene has a moderate melting point and high molecular weight(up to 38.2×10^(4)g·mol^(−1)),with a branching density distribution between 7 and 94 branches per 1000 carbons.More importantly,the polyethylene prepared by these catalysts exhibits excellent tensile properties,with strain and stress reaching 800%and 30 MPa,respectively.

3D printing encouraging desired in-situ polypyrrole seed-polymerization for ultra-high energy density supercapacitors

The tireless pursuit of supercapacitors with high energy density entails the parallel advancement of wellsuited electrode materials and elaborately engineered architectures.Polypyrrole(PPy)emerges as an exceedingly conductive polymer and a prospective pseudocapacitive materials for supercapacitors,yet the inferior cyclic stability and unpredictable polymerization patterns severely impede its real-world applicability.Here,for the first time,an innovative seed-induced in-situ polymerization assisted 3D printing strategy is proposed to fabricate PPy-reduced graphene oxide/poly(vinylidene difluoride-cohexafluoropropylene)(PVDF-HFP)(PPy-rGO/PH)electrodes with controllable polymerization behavior and exceptional areal mass loading.The preferred active sites uniformly pre-planted on the 3D-printed graphene substrates serve as reliable seeds to induce efficient polypyrrole deposition,achieving an impressive mass loading of 185.6 mg cm^(-2)(particularly 79.2 mg cm^(-2)for polypyrrole)and a superior areal capacitance of 25.2 F cm^(-2)at 2 mA cm^(-2)for a 12-layer electrode.In agreement with theses appealing features,an unprecedented areal energy density of 1.47 mW h cm^(-2)for a symmetrical device is registered,a rarely achieved value for other PPy/rGO-based supercapacitors.This work highlights a promising route to preparing high energy density energy storage modules for real-world applications.

Enhancing performance of low-temperature processed CsPbI2Br all-inorganic perovskite solar cells using polyethylene oxide-modified TiO_(2)

CsPbX_(3)-based(X=I,Br,Cl)inorganic perovskite solar cells(PSCs)prepared by low-temperature process have attracted much attention because of their low cost and excellent thermal stability.However,the high trap state density and serious charge recombination between low-temperature processed TiO_(2)film and inorganic perovskite layer interface seriously restrict the performance of all-inorganic PSCs.Here a thin polyethylene oxide(PEO)layer is employed to modify TiO_(2)film to passivate traps and promote carrier collection.The impacts of PEO layer on microstructure and photoelectric characteristics of TiO_(2)film and related devices are systematically studied.Characterization results suggest that PEO modification can reduce the surface roughness of TiO_(2)film,decrease its average surface potential,and passivate trap states.At optimal conditions,the champion efficiency of CsPbI_(2)Br PSCs with PEO-modified TiO_(2)(PEO-PSCs)has been improved to 11.24%from 9.03%of reference PSCs.Moreover,the hysteresis behavior and charge recombination have been suppressed in PEO-PSCs.

Ca and Sr co-doping induced oxygen vacancies in 3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts for boosting low-temperature oxidative coupling of methane

It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(A_(2)B_(2)O_(7)-type)catalysts with disordered defective cubic fluorite phased structure were successfully prepared by a colloidal crystal template method.3DOM structure promotes the accessibility of the gaseous reactants(O2and CH4)to the active sites.The co-doping of Ca and Sr ions in La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts improved the formation of oxygen vacancies,thereby leading to increased density of surface-active oxygen species(O_(2)^(-))for the activation of CH4and the formation of C2products(C2H6and C2H4).3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts exhibit high catalytic activity for OCM at low temperature.3DOM La1.7Sr0.3Ce1.7Ca0.3O7-δcatalyst with the highest density of O_(2)^(-)species exhibited the highest catalytic activity for low-temperature OCM,i.e.,its CH4conversion,selectivity and yield of C2products at 650℃are 32.2%,66.1%and 21.3%,respectively.The mechanism was proposed that the increase in surface oxygen vacancies induced by the co-doping of Ca and Sr ions boosts the key step of C-H bond breaking and C-C bond coupling in catalyzing low-temperature OCM.It is meaningful for the development of the low-temperature and high-efficient catalysts for OCM reaction in practical application.

Effect of solvent on the initiation mechanism of living anionic polymerization of styrene:A computational study

For living anionic polymerization(LAP),solvent has a great influence on both reaction mechanism and kinetics.In this work,by using the classical butyl lithium-styrene polymerization as a model system,the effect of solvent on the mechanism and kinetics of LAP was revealed through a strategy combining density functional theory(DFT)calculations and kinetic modeling.In terms of mechanism,it is found that the stronger the solvent polarity,the more electrons transfer from initiator to solvent through detailed energy decomposition analysis of electrostatic interactions between initiator and solvent molecules.Furthermore,we also found that the stronger the solvent polarity,the higher the monomer initiation energy barrier and the smaller the initiation rate coefficient.Counterintuitively,initiation is more favorable at lower temperatures based on the calculated results ofΔG_(TS).Finally,the kinetic characteristics in different solvents were further examined by kinetic modeling.It is found that in benzene and n-pentane,the polymerization rate exhibits first-order kinetics.While,slow initiation and fast propagation were observed in tetrahydrofuran(THF)due to the slow free ion formation rate,leading to a deviation from first-order kinetics.

Synthesis of Branched Polyethylene via Bulky α-Diimine Nickel(II)-Catalyzed Ethylene Chain-Walking Polymerization

The catalysis of olefin polymerization through the chain-walking process is a subject of great interest. In this contribution, the successful synthesis of a Brookhart-type unsymmetrical α-diimine nickel catalyst Ni, which contains both dibenzhydryl and phenyl groups, was determined by X-ray crystallography. The compound has a pseudo-tetrahedral geometry at the Ni center, showing pseudo-C2-symmetry. Upon activation with modified methylaluminoxane (MMAO), Ni1 exhibits high catalytic activity up to 1.02 × 107 g PE (mol Ni h)−1 toward ethylene polymerization, enabling the synthesis of high molecular weight branched polyethylene. The molecular weights and branching densities could be tuned over a very wide range. The polymerization results indicated the possibility of precise microstructure control, depending on the polymerization temperature. The branching densities were decreased with increasing the polymerization temperature.

Synthesis and Characterization of Poly Styrene-Co-Poly 2-Hydroxyethylmethacrylate (HEMA) Copolymer and an Investigation of Free-Radical Copolymerization Propagation Kinetics by Solvent Effects

A series of homo and copolymers of styrene (ST) and 2-hydroxyethyl methacrylate (HEMA) in three different media (bulk, tetrahydrofuran, and benzene) have been investigated by free radical polymerization method. The samples obtained from the synthesis were characterized by Fourier Transform-Infrared spectroscopy (FT-IR), proton nuclear magnetic resonance spectroscopy (1H NMR), atomic force microscopy (AFM), and differential scanning calorimetry (DSC). The results show that the synthesis of the polymers is more feasible under neat conditions rather than solvent directed reaction. Moreover, the DSC data shows that the polystyrene obtained is amorphous in nature and therefore displayed only a glass transition signal rather than crystallization and melting peaks. In addition, this study indicates that homolopolymerization of styrene via free radical polymerization tends to be preferable in less polar solvents like THF than in non-polar solvents like benzene. Benzene might destabilize the formation of the reactive radicals leading to the formation of the products. In summary, the homolpolymerization of styrene is more feasible than the homopolymerization 2-hydroxyethyl methacrylate under the experimental setup used. Styrene is more reactive than 2-hydroxyethyl methacrylate than free radical polymerization reaction due in part of the generation of the benzylic radical intermediate which is more stable leading to the formation of products than alkyl radical which are less stable. Furthermore, polymerization of styrene under neat conditions is preferable in solvent-assisted environments. The choice of solvent for the synthesis of these polymers is crucial and therefore the selection of solvent that leads to the formation of a more stable reaction intermediate is more favorable. It is worth noting that the structure of the proposed copolymer consists of a highly polar and hydrophilic monomer, 2-hydroxyethyl methacrylate and a highly non-polar and hydrophobic monomer, styrene. These functionalities constitute an amphiphilic copolymer with diverse characteristics. A plausible explanation underlying our observations is that the reaction conditions employed in the synthesis of these copolymers might not be the right route required under free radical polymerization.

Perspective on low-temperature electrolytes for LiFePO 4-based lithium-ion batteries

The olivine-type lithium iron phosphate(LiFePO_(4))cathode material is promising and widely used as a high-performance lithium-ion battery cathode material in commercial batteries due to its low cost,environmental friendliness,and high safety.At present,LiFePO_(4)/C sec-ondary batteries are widely used for electronic products,automotive power batteries,and other occasion-related applications with good thermal stability,stable cycle performance,and low room-temperature self-discharge rate.However,LiFePO_(4)-based battery applications are seriously limited when they are operated in a cold climate.This outcome is due to a considerable decrease in Li+transport capabilities within the elec-trode,particularly leading to a dramatic decrease in the electrochemical capacity and power performance of the electrolyte.Therefore,the design of low-temperature electrolytes is important for the further commercial application of LiFePO_(4) batteries.This paper reviews the key factors for the poor low-temperature performance of LiFePO_(4)-based batteries and the research progress of low-temperature electrolytes.Spe-cial attention is paid to electrolyte components,including lithium salts,cosolvents,additives,and the development of new electrolytes.The factors affecting the anode are also analyzed.Finally,according to the current research progress,some viewpoints are summarized to provide suitable modification methods and research suggestions for improving the practicability of LiFePO_(4)/C commercial batteries at low temperat-ures in the future.

Screening non-noble metal oxides to boost the low-temperature combustion of polyethylene waste in air

Globally,the efficient utilization of polymer wastes is one of the most important issues for current sustainable development topics.Herein,a green and efficient low-temperature combustion approach is proposed to deal with polymer wastes and recover heat energy,simultaneously alleviating the environment and energy crisis.Non-noble metal oxides(Al_(2)O_(3),Fe_(2)O_(3),NiO_(2),ZrO_(2),La_(2)O_(3)and CeO_(2)) were prepared,characterized and screened to boost the low-temperature combustion of polyethylene waste at 300℃ in air.The mass change,heat release and CO_(x) formation were studied in details and employed to evaluate the combustion rate and efficiency.It was found that CeO_(2)significantly enhanced the combustion rate and efficiency,which was respectively 2 and 7 times that of non-catalytic case.An interesting phenomenon was observed that the catalytic performance of CeO_(2) in polyethylene low-temperature combustion was significantly improved by the 7-day storage in the room environment or water treatment.XPS analysis confirmed the co-existence of Ce^(3+) and Ce^(4+) in CeO_(2),and the 7-day storage and water treatment promoted the amount of Ce^(3+),which facilitated the formation of the oxygen vacancies.That may be the reason why CeO_(2) exhibited excellent catalytic performance in polyethylene low-temperature combustion.

Involvement of long non-coding RNAs in pear fruit senescence under high-and low-temperature conditions

Pear fruit senescence under high-and low-temperature conditions has been reported to be mediated by microRNAs.Long non-coding RNAs(lncRNAs),which can function as competing endogenous RNAs that interact with microRNAs,may also be involved in temperature-affected fruit senescence.Based on the transcriptome and microRNA sequencings,in this study,3330 lncRNAs were isolated from Pyrus pyrifolia fruit.Of these lncRNAs,2060 and 537 were responsive to high-and low-temperature conditions,respectively.Of these differentially expressed lncRNAs,82 and 24 correlated to the mRNAs involved in fruit senescence under high-and low-temperature conditions,respectively.Moreover,three lncRNAs were predicted to be competing endogenous RNAs(ceRNAs)that interact with the microRNAs involved in fruit senescence,while one and two ceRNAs were involved in fruit senescence under high-and low-temperature conditions,respectively.A dual-luciferase assay showed that the interaction of an lncRNA with a microRNA disrupts the action of the microRNA on the expression of its target mRNA(s).Furthermore,four alternative splicing-derived lncRNAs interacted with miR172i homologies(Novel_88 and Novel_69)to relieve the repressed expression of their target and produce an miR172i precursor.Correlation analysis of microRNA expression suggested that Novel_69 is likely involved in the cleavage of the pre-miR172i hairpin to generate mature miR172i.Taken together,lncRNAs are involved in pear fruit senescence under high-or low-temperature conditions through ceRNAs and the production of microRNA.

Low-temperatures synthesis of CuS nanospheres as cathode material for magnesium second batteries

Rechargeable magnesium batteries(RMBs),as one of the most promising candidates for efficient energy storage devices with high energy,power density and high safety,have attracted increasing attention.However,searching for suitable cathode materials with fast diffusion kinetics and exploring their magnesium storage mechanisms remains a great challenge.Cu S submicron spheres,made by a facile low-temperature synthesis strategy,were applied as the high-performance cathode for RMBs in this work,which can deliver a high specific capacity of 396mAh g^(-1)at 20 mA g^(-1) and a remarkable rate capacity of 250 m Ah g^(-1)at 1000 mA g^(-1).The excellent rate performance can be assigned to the nano needle-like particles on the surface of Cu S submicron spheres,which can facilitate the diffusion kinetics of Mg^(2+).Further storage mechanism investigations illustrate that the Cu S cathodes experience a two-step conversion reaction controlled by diffusion during the electrochemical reaction process.This work could make a contribution to the study of the enhancement of diffusion kinetics of Mg2+and the reaction mechanism of RMBs.

Low-Temperature Carbonized Nitrogen-Doped Hard Carbon Nanofiber Toward High-Performance Sodium-Ion Capacitors

Carbon nanofiber(CNF)was widely utilized in the field of electrochemical energy storage due to its superiority of conductivity and mechanics.However,CNF was generally prepared at relatively high temperature.Herein,nitrogen-doped hard carbon nanofibers(NHCNFs)were prepared by a lowtemperature carbonization treatment assisted with electrospinning technology.Density functional theory analysis elucidates the incorporation of nitrogen heteroatoms with various chemical states into carbon matrix would significantly alter the total electronic configurations,leading to the robust adsorption and efficient diffusion of Na atoms on electrode interface.The obtained material carbonized at 600°C(NHCNF-600)presented a reversible specific capacity of 191.0 mAh g^(−1)and no capacity decay after 200 cycles at 1 A g^(−1).It was found that the sodium-intercalated degree had a correlation with the electrochemical impedance.A sodium-intercalated potential of 0.2 V was adopted to lower the electrochemical impedance.The constructed sodium-ion capacitor with activated carbon cathode and presodiated NHCNF-600 anode can present an energy power density of 82.1 Wh kg^(−1)and a power density of 7.0 kW kg^(−1).

Mechanistically Novel Frontal-Inspired In Situ Photopolymerization:An Efficient Electrode|Electrolyte Interface Engineering Method for High Energy Lithium Metal Polymer Batteries

The solvent-free in situ polymerization technique has the potential to tailor-make conformal interfaces that are essential for developing durable and safe lithium metal polymer batteries(LMPBs).Hence,much attention has been given to the eco-friendly and rapid ultraviolet(UV)-induced in situ photopolymerization process to prepare solid-state polymer electrolytes.In this respect,an innovative method is proposed here to overcome the challenges of UV-induced photopolymerization(UV-curing)in the zones where UV-light cannot penetrate,especially in LMPBs where thick electrodes are used.The proposed frontal-inspired photopolymerization(FIPP)process is a diverged frontal-based technique that uses two classes(dual)of initiators to improve the slow reaction kinetics of allyl-based monomers/oligomers by at least 50%compared with the conventional UV-curing process.The possible reaction mechanism occurring in FIPP is demonstrated using density functional theory calculations and spectroscopic investigations.Indeed,the initiation mechanism identified for the FIPP relies on a photochemical pathway rather than an exothermic propagating front forms during the UV-irradiation step as the case with the classical frontal photopolymerization technique.Besides,the FIPP-based in situ cell fabrication using dual initiators is advantageous over both the sandwich cell assembly and conventional in situ photopolymerization in overcoming the limitations of mass transport and active material utilization in high energy and high power LMPBs that use thick electrodes.Furthermore,the LMPB cells fabricated using the in situ-FIPP process with high mass loading LiFePO_(4)electrodes(5.2 mg cm^(-2))demonstrate higher rate capability,and a 50%increase in specific capacity against a sandwich cell encouraging the use of this innovative process in large-scale solid-state battery production.

Triggering dynamics of acetylene topochemical polymerization

Topochemical reactions are a promising method to obtain crystalline polymeric materials with distance-determined regio-or stereoselectivity.It has been concluded on an empirical basis that the closest intermolecular C⋅⋅⋅C distance in crystals of alkynes,d(C⋅⋅⋅C)min,should reach a threshold of∼3Åfor bonding to occur at room temperature.To understand this empirical threshold,we study here the polymerization of acetylene in the crystalline state under high pressure by calculating the structural geometry,vibrational modes,and reaction profile.We find d(C⋅⋅⋅C)min to be the sum of an intrinsic threshold of 2.3Åand a thermal displacement of 0.8Å(at room temperature).Molecules at the empirical threshold move via several phonon modes to reach the intrinsic threshold,at which the intermolecular electronic interaction is sharply enhanced and bonding commences.A distance–vibration-based reaction picture is thus demonstrated,which provides a basis for the prediction and design of topochemical reactions,as well as an enhanced understanding of the bonding process in solids.