Fluctuations in equine cutaneous pH and transepidermal water loss with time of day and ambient conditions.

Cutaneous pH and transepidermal water loss (TEWL) are commonly utilized measures in dermatological research as they provide information concerning barrier function. The importance of dermal health has become more evident in recent years. Accordingly, the aim of this work was to identify natural fluctuations in the biophysical parameters of healthy equine skin. Cutaneous pH and TEWL was collected on nine mares at 6:00 AM, 12:00 PM, and 6:00 PM daily for five days on the nose, withers, girth area, mid-back, and base of tail. Ambient temperature and humidity were measured at each collection. Statistical analysis was completed using SAS On Demand. Tests included repeated measures, ANOVA, and regression analysis. Mean cutaneous pH significantly differed by day (P = 0.0052) and time (P = 0.0073) but was unaffected by anatomical location (P = 0.2841). Interestingly, cutaneous pH had a significant interaction of day and location (P = 0.0004). Mean TEWL measures significantly differed by day (P < 0.0001), time (P < 0.0001), and anatomical location (P = 0.0231). Interaction of day and time had a significant effect on TEWL (P < 0.0001) and also resulted in a three-way interaction of day, time, and location (P = 0.0167). There were no significant associations of pH with temperature and humidity. All measures of TEWL across all locations were significantly correlated with temperature and humidity (P < 0.0001). Cutaneous pH and TEWL measures are affected by environmental conditions which should be considered in future models and work using dermal characteristics of horses.

Electrochemical Nitrogen Reduction to Ammonia at Ambient Condition on the (111) Facets of Transition Metal Carbonitrides.

We conducted Density Functional Theory calculations to investigate a class of materials with the goal of enabling nitrogen activation and electrochemical ammonia production under ambient conditions. The source of protons at the anode could originate from either water splitting or H2, but our specific focus was on the cathode reaction, where nitrogen is reduced into ammonia. We examined the conventional associative mechanism, dissociative mechanism, and Mars-van Krevelen mechanism on the (111) facets of the NaCl-type structure found in early transition metal carbonitrides, including Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, Sc, Y, and W. We explored the catalytic activity by calculating the free energy of all intermediates along the reaction pathway and constructing free energy diagrams to identify the steps that determine the reaction's feasibility. Additionally, we closely examined the potential for catalyst poisoning within the electrochemical environment, considering the bias required to drive the reaction. Furthermore, we assessed the likelihood of catalyst decomposition and the potential for catalyst regeneration among the most intriguing carbonitrides. Our findings revealed that the only carbonitride catalyst considered here exhibiting both activity and stability, capable of self-regeneration and nitrogen-to-ammonia activation, is NbCN with a low potential-determining step energy of 0.58 eV. This material can facilitate ammonia formation via a mixed associative-MvK mechanism. In contrast, other carbonitrides of this crystallographic orientation are likely to undergo decomposition, reverting to their parent metals under operational conditions.

Contact-Electro-Catalysis for Direct Oxidation of Methane under Ambient Conditions.

The conversion of methane under ambient conditions has attracted significant attention. Although advancements have been made using active oxygen species from photo- and electro- chemical processes, challenges such as complex catalyst design, costly oxidants, and unwanted byproducts remain. This study exploits the concept of contact-electro-catalysis, initiating chemical reactions through charge exchange at a solid-liquid interface, to report a novel process for directly converting methane under ambient conditions. Utilizing the electrification of commercially available Fluorinated Ethylene Propylene (FEP) with water under ultrasound, we demonstrate how this interaction promote the activation of methane and oxygen molecules. Our results show that the yield of HCHO and CH3OH can reach 467.5 and 151.2 µmol ⋅ gcat -1, respectively. We utilized electron paramagnetic resonance (EPR) to confirm the evolution of hydroxyl radicals (⋅OH) and superoxide radicals (⋅OOH). Isotope mass spectrometry (MS) was employed to analyze the elemental origin of CH3OH, which can be further oxidized to HCHO. Additionally, we conducted density functional theory (DFT) simulations to assess the reaction energies of FEP with H2O, O2, and CH4 under these conditions. The implications of this methodology, with its potential applicability to a wider array of gas-phase catalytic reactions, underscore a significant advance in catalysis.

Pyrene-Based Nanoporous Covalent Organic Framework for Carboxylation of C-H Bonds with CO2 and Value-Added 2-Oxazolidinones Synthesis under Ambient Conditions.

The selective carbon capture and utilization (CCU) as a one-carbon (C1) feedstock offers dual advantages for mitigating the rising atmospheric CO2 content and producing fine chemicals/fuels. In this context, herein, we report the application of a porous bipyridine-functionalized, pyrene-based covalent organic framework (Pybpy-COF) for the stable anchoring of catalytic Ag(0) nanoparticles (NPs) and its catalytic investigation for fixation of CO2 to commodity chemicals at ambient conditions. Notably, Ag@Pybpy-COF showed excellent catalytic activity for the carboxylation of various terminal alkynes to corresponding alkynyl carboxylic acids/phenylpropiolic acids via C-H bond activation under atmospheric pressure conditions. Besides, carboxylative cyclization of various propargylic amines with CO2 to generate 2-oxazolidinones, an important class of antibiotics, has also been achieved under mild conditions. This significant catalytic activity of Ag@Pybpy-COF with wide functional group tolerance is rendered by the presence of highly exposed, alkynophilic Ag(0) catalytic sites decorated on the pore walls of high surface area (787 m2 g-1) Pybpy-COF. Further, density functional theory calculations unveiled the detailed mechanistic path of the Ag@Pybpy-COF-catalyzed transformation of CO2 to alkynyl carboxylic acids and 2-oxazolidinones. Moreover, the catalyst showed high recyclability for several cycles of reuse without significant loss in its catalytic activity and structural rigidity. This work demonstrates the promising application of Pybpy-COF for stable anchoring of Ag NPs for successful transformation of CO2 to valuable commodity chemicals at ambient conditions.

Synthesis of Ultra-Incompressible and Recoverable Carbon Nitrides Featuring CN4 Tetrahedra.

Carbon nitrides featuring three-dimensional frameworks of CN4 tetrahedra are one of the great aspirations of materials science, expected to have a hardness greater than or comparable to diamond. After more than three decades of efforts to synthesize them, no unambiguous evidence of their existence has been delivered. Here, the high-pressure high-temperature synthesis of three carbon-nitrogen compounds, tI14-C3 N4 , hP126-C3 N4 , and tI24-CN2 , in laser-heated diamond anvil cells, is reported. Their structures are solved and refined using synchrotron single-crystal X-ray diffraction. Physical properties investigations show that these strongly covalently bonded materials, ultra-incompressible and superhard, also possess high energy density, piezoelectric, and photoluminescence properties. The novel carbon nitrides are unique among high-pressure materials, as being produced above 100 GPa they are recoverable in air at ambient conditions.

Impact of color temperature and illuminance of ambient light conditions on the accuracy of complete-arch digital implant scans.

OBJECTIVE: The purpose of the present study was to assess the influence of color temperature and illuminance of ambient light on the accuracy of different intraoral scanners (IOSs) in complete-arch implant scans. METHODS: An edentulous model with six implants and scan bodies was digitized by using a laboratory scanner (DW-7-140; Dental Wings) to obtain a reference mesh. Fifteen scans were performed employing two intraoral scanners (Trios 4;3Shape A/S and i700; Medit Co) at two illuminances (500 and 1000 lux) and three color temperatures (3200, 4400, and 5600 K). Scanning accuracy was measured by using a 3D metrology software program (Geomagic Control X). Kruskal-Wallis, one-way ANOVA, and pairwise comparison tests were used to analyze the data (α = .05). RESULTS: Significant differences in trueness and precision values were found among the different IOSs under the same ambient lighting condition and among the different lighting conditions for a given IOS (p < .05) except for trueness in i700 groups (p > .05). CONCLUSIONS: The influence on the accuracy of color temperature and illuminance varied depending on the intraoral scanner. An optimal ambient scanning light condition was not found; this should be adjusted based on the specific IOS system used. 3200 K of ambient light influences the precision of i700 when performed at 1000 lux, decreasing the accuracy. The variation of color temperature at the same illuminance does not affect the scanning accuracy of TRIOS 4, which obtained better accuracy in all scans at 1000 lux.

Evaporation issues of acoustically levitated fuel droplets.

Fuel droplet evaporation is essential to the generation of flammable mixtures in thermal engines. Generally, liquid fuel is injected directly into the hot, high-pressure atmosphere to form scattered droplets. Many investigations on droplet evaporation have been conducted with techniques involving the influence of boundaries, such as suspended wires. Ultrasonic levitation is a non-contact and non-destructive technology that can avoid the impact of hanging wire on droplet shape and heat transfer. Besides, it can simultaneously levitate multiple droplets and allow them to associate with each other or be used to study droplet instability behaviors. This paper reviews the influences of the acoustic field on levitated droplets, the evaporation characteristics of acoustically levitated droplets, and the prospects and limitations of ultrasonic suspension methods for droplet evaporation, which can serve as references for relevant studies.

2,2,2-Trifluoroethanol-Assisted Construction of 2D/3D Perovskite Heterostructures for Efficient and Stable Perovskite Solar Cells Made in Ambient Air.

To achieve future commercialization of perovskite solar cells (PSCs), balancing the efficiency, stability, and manufacturing cost is required. In this study, we develop an air processing strategy for efficient and stable PSCs based on 2D/3D heterostructures. The organic halide salt phenethylammonium iodide is adopted to in situ construct a 2D/3D perovskite heterostructure, in which 2,2,2-trifluoroethanol as a precursor solvent is introduced to recrystallize 3D perovskite and form an intermixed 2D/3D perovskite phase. This strategy simultaneously passivates defects, reduces nonradiative recombination, prevents carrier quenching, and improves carrier transport. As a result, a champion power conversion efficiency of 20.86% is obtained for air-processed PSCs based on 2D/3D heterostructures. Moreover, the optimized devices exhibit superior stability, remaining more than 91 and 88% of their initial efficiencies after 1800 h of storage under dark condition and 24 h of continuous heating at 100 °C, respectively. Our study provides a convenient method to fabricate all-air-processed PSCs with high efficiency and stability.

Single atomic cerium sites anchored on nitrogen-doped hollow carbon spheres for highly selective electroreduction of nitric oxide to ammonia.

Electrocatalytic nitric oxide reduction reaction (NORR) at ambient environments not only offers a promising strategy to yield ammonia (NH3) but also degrades the NO contaminant; however, its application depends on searching for high-performance catalysts. Herein, we present single atomic Ce sites anchored on nitrogen-doped hollow carbon spheres that are capable of electro-catalyzing NO reduction to NH3 in an acidic solution, achieving a maximal Faradaic efficiency of 91 % and a yield rate of 1023 µg h-1 mgcat.-1 at -0.7 V vs RHE for NH3 formation, both of which outperform these on Ce nanoclusters and approach the best-reported results. Meanwhile, the single atomic Ce catalyst shows good structural and electrochemical stability during the 30-h NO electrolysis. Furthermore, when the single atomic Ce catalyst was used as cathodic material in a proof-of-concept of Zn-NO battery, it delivers a maximal power density of 3.4 mW cm-2 and a high NH3 yield rate of 309 µg h-1 mgcat.-1. Theoretical simulations suggest that the Ce-N4 active moiety can not only activate NO molecules via a strong electronic interaction but also reduce the free energy barrier of *NO transition to *NOH intermediate as the limiting step, and therefore boosting the NORR kinetics and suppressing the competitive hydrogen evolution.

Hydrogenation Reactions with Synergistic Catalysis of Pd single atoms and nanoparticles under Near-Ambient Conditions.

Due to the limited resources and high cost of noble metals, boosting their catalytic activities is highly desired in the current catalysis industry. Here, we report a synergetic catalyst, combining Pd2+ and Pd0 species in a nitrogen-doped porous carbons (NPC), which shows boosted catalytic activities in hydrogenation reactions of organic nitro compounds (nitrobenzene, 4-nitrophenol, 1-nitronaphthalene and 1-nitropropane) under near ambient conditions. This synergetic catalyst NPC-[Pd] was synthesized by partial reduction of a palladium-loaded NPC. The catalytic activities and selectivity of NPC-[Pd] for hydrogenation were enhanced significantly compared with those of NPC-Pd2+ or NPC-Pd0 nanoparticles. Theoretical calculations show that H2 preferentially dissociates on Pd nanoparticles, and then organic molecules (nitrobenzene) can be captured and react with the dissociated H atom on Pd2+ sites. Similar reaction procedure also occur on Pt or Rh. Hydrogenation of different aromatic compounds with different functional groups (naphthalene, 4-nitrochlorobenzene, benzaldehyde and acetophenone) confirmed the broad excellent catalytic activity of this synergistic catalyst.

One-Pot Synthesis of Ruthenium-Based Nanocatalyst Using Reduced Graphene Oxide as Matrix for Electrochemical Synthesis of Ammonia.

Conventional ammonia production consumes significant energy and causes enormous carbon dioxide (CO2) emissions globally. To lower energy consumption and mitigate CO2 emissions, a facile, environmentally friendly, and cost-effective one-pot method for the synthesis of a ruthenium-based nitrogen reduction nanocatalyst has been developed using reduced graphene oxide (rGO) as a matrix. The nanocatalyst synthesis was based on a single-step simultaneous reduction of RuCl3 into ruthenium-based nanoparticles (Ru-based NPs) and graphene oxide (GO) into rGO using glucose as the reducing agent and stabilizer. The obtained ruthenium-based nanocatalyst with rGO as a matrix (Runano-based/rGO) has shown much higher catalytic activity at lower temperatures and pressures for ammonia synthesis than conventional iron catalysts. The rGO worked as a promising promoter for the electrochemical synthesis of ammonia due to its excellent electrical and thermal conductivity. The developed Runano-based/rGO nanocatalyst was characterized using transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), ultraviolet-visible (UV-vis) absorption spectroscopy, X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), dynamic light scattering (DLS), inductively coupled plasma mass spectrometry (ICP-MS), and X-ray photoelectron spectroscopy (XPS). The results demonstrated that the size of the Ru-based NPs on the surface of rGO was 1.9 ± 0.2 nm and the ruthenium content was 25.03 wt %. Bulk electrolysis measurements were conducted on thin-layer electrodes at various cathodic potentials in a N2-saturated 0.1 M H2SO4 electrolyte at room temperature. From the chronoamperometric measurements, the maximum faradic efficiency (F.E.) of 2.1% for ammonia production on the nanostructured Runano-based/rGO electrocatalyst was achieved at a potential of -0.20 V vs reversible hydrogen electrode (RHE). This electrocatalyst has attained a superior ammonia production rate of 9.14 µg·h-1·mgcat.-1. The results demonstrate the feasibility of reducing N2 into ammonia under ambient conditions and warrant further exploration of the nanostructured Runano-based/rGO for electrochemical ammonia synthesis.

Relationship Between Mass Loss and Fruit Quality of Sweet Orange at Two Different Storage Conditions.

Mass loss from fresh produce is linked to a reduction of its aesthetic value. However, a relationship between mass loss and biochemical quality parameters at different storage conditions has not been widely explored. Therefore, the current study is designed with the objectives to determine the behavior of fruit quality parameters and a relationship between fruit mass loss and fruit quality at two different storage conditions. Sweet orange fruit stored in a zero energy cool chamber (ZECC) had greater shelf-life of more than 15 days, fruit size (62.40 mm) and peel (35.15%) and lower mass loss (4.94%), juice (32.19%) and electrical conductivity (EC) (2.06 S/m) as compared to ambient conditions in laboratory during 25 days of storage. In ZECC, only EC was positively correlated (r = 0.57) with mass loss, whereas at room temperature EC (r = 0.76), total soluble solids (TSS) (r = 0.60) and fruit internal temperature (r = 0.64) were positively and peel (%) (r = -0.52) and fruit diameter (r = -0.49) were negatively correlated with mass loss. Correlation of combined storage conditions revealed that EC (r = 0.47) and TSS (r = 0.50) were positively and peel (%) (r = -0.77) and fruit diameter (r = -0.55) were negatively correlated with mass loss (%). The principal component analysis (PCA) revealed that the scores of room temperature were strongly associated with TSS, pH, EC, mass loss (%), juice (%) and internal temperature (°C), whereas scores of ZECC were strongly associated with pulp (%), ascorbic acid (mg 100 mL-1), acidity (%), and fruit diameter (mm).

Plastics-to-syngas photocatalysed by Co-Ga2O3 nanosheets.

Plastics take hundreds of years to degrade naturally, while their chemical degradation typically requires high temperature and pressure. Here, we first utilize solar energy to realize the sustainable and efficient plastic-to-syngas conversion with the aid of water at ambient conditions. As an example, the commercial plastic bags could be efficiently photoconverted into renewable syngas by Co-Ga2O3 nanosheets, with hydrogen and carbon monoxide formation rates of 647.8 and 158.3 µmol g-1 h-1. In situ characterizations and labelling experiments unveil water is photoreduced into hydrogen, while non-recyclable plastics including polyethylene bags, polypropylene boxes and polyethylene terephthalate bottles are photodegraded into carbon dioxide, which is further selectively photoreduced into carbon monoxide. In-depth investigation illustrates that the efficiency of syngas production mainly depends on the carbon dioxide reduction process and hence photocatalysts of high carbon dioxide reduction activity should be designed to promote the efficiency of plastic-to-syngas conversion in the future. The concept for the photoreforming of non-recyclable plastics into renewable syngas helps to eradicate 'white pollution' and alleviate the energy crisis simultaneously.

Rational Design of Synergistic Structure Between Single-Atoms and Nanoparticles for CO2 Hydrogenation to Formate Under Ambient Conditions.

Single-atom catalysts (SACs) as the new frontier in heterogeneous catalysis have attracted increasing attention. However, the rational design of SACs with high catalytic activities for specified reactions still remains challenging. Herein, we report the rational design of a Pd1-PdNPs synergistic structure on 2,6-pyridinedicarbonitrile-derived covalent triazine framework (CTF) as an efficient active site for CO2 hydrogenation to formate under ambient conditions. Compared with the catalysts mainly comprising Pd1 and PdNPs, this hybrid catalyst presented significantly improved catalytic activity. By regulating the ratio of Pd1 to PdNPs, we obtained the optimal catalytic activity with a formate formation rate of 3.66 molHCOOM·molPd -1·h-1 under ambient conditions (30°C, 0.1 MPa). Moreover, as a heterogeneous catalyst, this hybrid catalyst is easily recovered and exhibits about a 20% decrease in the catalytic activity after five cycles. These findings are significant in elucidating new rational design principles for CO2 hydrogenation catalysts with superior activity and may open up the possibilities of converting CO2 under ambient conditions.

Ferromagnetic-Based Charge-Accumulation Triboelectric Nanogenerator With Ultrahigh Surface Charge Density.

An encouraging micro-energy harvesting technology, the triboelectric nanogenerator (TENG), has been proven to transfer ambient environmental micro-energy into electricity, but a low surface charge density results in low performance and limits the practical application of TENG. Here, a ferromagnetic-based charge-accumulation TENG (FC-TENG) is proposed with ultrahigh surface charge density and performances. The FC-TENG introduces a ferromagnetic media to enhance the output charge by magnetization effect. Meanwhile, the charge can also be continuously accumulated by the charge pump effects. Based on these two effects, an ultra-high surface charge density of 2.85 mC m-2 is obtained under ambient atmospheric conditions using an ultra-thin PET film (3 µm) and deposited Permalloy ferromagnetic electrodes. Meanwhile, the surface charge density of the FC-TENG can always maintain more than 1.5 mC m-2 , even if the relative humidity arrives at 90%. This work provides a prospective technical mode to enhance the surface charge density of TENG, which would shed a new insight and guidance on the high-performance TENG for various environmental conditions such as the ocean, industrial manufacturing, aerospace, and rail traffic.

Analysis of airborne sputum droplets flow dynamic behaviors under different ambient conditions and aerosol size effects.

The coronavirus (COVID-19) is becoming more threatening with the emergence of new mutations. New virus transmission and infection processes remain challenging and re-examinations of proper protection methods are urgently needed. From fluid dynamic viewpoint, the transmission of virus-carrying droplets and aerosols is one key to understanding the virus-transmission mechanisms. This study shows virus transmission by incorporating flow-evaporation model into the Navier-Stokes equation to describe the group of airborne sputum droplets exhaled under Rosin-Rammler distribution. Solid components and humidity field evolution are incorporated in describing droplet and ambient conditions. The numerical model is solved by an inhouse code using advection-diffusion equation for the temperature field and the humidity field, discretized by applying the total-variation diminishing Runge-Kutta method. The results of this study are presented in detail to show the different trends under various ambient conditions and to reveal the major viral-transmission routes as a function of droplet size.

Oxygen-Demanding Photocontrolled RAFT Polymerization Under Ambient Conditions.

A photocontrolled reversible addition-fragmentation chain transfer (RAFT) process is developed by initiating polymerization through a 1,3-diaminopropane-triethylborane (DAPTB)-diphenyl iodonium salt (Ph2 I+ ) complex (DAPTB/Ph2 I+ ) under ambient temperature and atmospheric conditions. Upon demand, this air-stable DAPTB/Ph2 I+ complex is photolyzed to liberate a reactive triethylborane that consumes atmospheric oxygen and generates ethyl radicals, which initiate and mediate RAFT polymerization. Controlled RAFT polymerization is thus achieved without any prior deoxygenation using a novel RAFT chain transfer agent, BP-FSBC, which contains both benzophenone and sulfonyl fluoride moieties. Furthermore, the kinetics of polymerization reveal that the reaction process is rapid, and well-defined polymers are produced by a 61% conversion of 2-hydroxyethyl acrylate (HEA) within 7 min and 77% conversion of N,N-dimethylacrylamide (DMA) within 10.5 min. The temporal and spatial control of this photopolymerization is also demonstrated by an "on/off" switch of UV irradiation and a painting-on-a-surface approach, respectively. In addition, active chain ends are demonstrated by preparing block copolymers by chain extension and click sulfur(VI)-fluoride exchange postreaction using RAFT-derived macrochain transfer agents.

Use of a miniature diamond-anvil cell in a joint X-ray and neutron high-pressure study on copper sulfate pentahydrate.

Single-crystal X-ray and neutron diffraction data are usually collected using separate samples. This is a disadvantage when the sample is studied at high pressure because it is very difficult to achieve exactly the same pressure in two separate experiments, especially if the neutron data are collected using Laue methods where precise absolute values of the unit-cell dimensions cannot be measured to check how close the pressures are. In this study, diffraction data have been collected under the same conditions on the same sample of copper(II) sulfate pentahydrate, using a conventional laboratory diffractometer and source for the X-ray measurements and the Koala single-crystal Laue diffractometer at the ANSTO facility for the neutron measurements. The sample, of dimensions 0.40 × 0.22 × 0.20 mm3 and held at a pressure of 0.71 GPa, was contained in a miniature Merrill-Bassett diamond-anvil cell. The highly penetrating diffracted neutron beams passing through the metal body of the miniature cell as well as through the diamonds yielded data suitable for structure refinement, and compensated for the low completeness of the X-ray measurements, which was only 24% on account of the triclinic symmetry of the sample and the shading of reciprocal space by the cell. The two data-sets were combined in a single 'XN' structure refinement in which all atoms, including H atoms, were refined with anisotropic displacement parameters. The precision of the structural parameters was improved by a factor of up to 50% in the XN refinement compared with refinements using the X-ray or neutron data separately.

Amino-Linked Conjugated Tetrazole Ring Passivation Strategy for Air-Processed Perovskite Cells with Predominant Stability and Efficiency.

Perovskite solar cells (PSCs) develop rapidly with certified efficiency over 25.5 %, but there are remaining problems such as defects-induced recombination and degradation throughout the whole device. Functional organic small molecule passivation strategies are diverse and efficient, enhancing the efficiency and stability of PSCs. Here, 5-aminotetrazole (5ATZ) was introduced for the first time as an effective passivator, where -NH2 and -NH as active sites interacted with the Pb and I related to vacancy defects in perovskites, anchoring defects and preventing further unavoidable ion migration and device degradation. Furthermore, the extensive π-electron delocalization around the tetrazole conjugated ring significantly promoted the charge transfer. Therefore, the 5ATZ-processed PSCs provided enhanced voltage and current, showed superior 19.75 % power conversion efficiency with excellent performance and improved stability, and demonstrated one of the best performances in all-air preparation to date. The simultaneous multi-effect passivation strategy of vacancy defects in perovskites will contribute to eliminate obstacles on the road to commercialization of PSCs.

Synthesis of Diverse Polycarbonates by Organocatalytic Copolymerization of CO2 and Epoxides: From High Pressure and Temperature to Ambient Conditions.

Organophosphazenes combined with triethylborane (TEB) were selected as binary organocatalyts for the copolymerization of CO2 and epoxides. Both the activity and selectivity were highly dependent on the nature of phosphazenes. 2,4,6-Tris[tri(1-pyrrolidinyl)-iminophosphorane]-1,3,5-triazine (C3 N3 -Py-P3 ) with a relatively low basicity (pKa =26.5 in CD3 CN) and a bulky molecular size (φ=1.3 nm) exhibited an unprecedented efficiency (TON up to 12240) and selectivity (>99 % polymer selectivity and >99 % carbonate linkages) toward copolymerization of CO2 and cyclohexene oxide (CHO), and produced CO2 -based polycarbonates (CO2 -PCs) with high molar masses (Mn up to 275.5 kDa) at 1 MPa of CO2 and 80 °C. Surprisingly, this binary catalytic system achieved efficient CO2 /CHO copolymerization with TOF up to 95 h-1 at 1 atm pressure and room temperature.