Interaction of CO2 gas with silicone elastomer at high ambient pressures

Interaction of high-pressure CO₂ gas with a silicone elastomer, and to a lesser extent, with a nitrile rubber and a PTFE have been investigated. Sorptive dilations of the polymers were measured with the help of custom-made piezoelectric ultrasonic transducers under gas pressures of up to ca. 22 MPa at 42°C. The gas mass sorption was determined by a vibrating reed probe. For the silicone elastomer system the dilation isotherm mimics the sorption isotherm. The partial molar volume (PMV) of the absorbed CO₂ gas in the silicone elastomer has been computed. A significant drop in the PMV value is observed when the CO₂ gas becomes supercritical. In the transition region, the transmission of ultrasonic signals through the specimen indicated the formation of discrete small (estimated as about 60 μm in diameter) high density zones of CO₂ in the rubber matrix. The plasticization effects of the absorbed high pressure CO₂ gas have been identified from the interpretation of the changes in the acoustic longitudinal modulus obtained from ultrasonic transmission measurements. The effects of rapid gas decompression on the structural integrity of the various polymers have also been determined. Significant inflation of certain specimens occur toward the latter stages of the decompression cycle. The initiation and development of internal cracks or bubbles was followed by monitoring the ultrasonic signal attenuation.     

Tailoring of nanoscale porosity in carbide-derived carbons for hydrogen storage

The poor performance of hydrogen storage materials continues to hinder development of fuel cell-powered automobiles. Nanoscale carbons, in particular (activated carbon, exfoliated graphite, fullerenes, nanotubes, nanofibers, and nanohorns), have not fulfilled their initial promise. Here we show that carbon materials can be rationally designed for H2 storage. Carbide-derived carbons (CDC), a largely unknown class of porous carbons, are produced by high-temperature chlorination of carbides. Metals and metalloids are removed as chlorides, leaving behind a collapsed noncrystalline carbon with up to 80% open pore volume. The detailed nature of the porosity-average size and size distribution, shape, and total specific surface area (SSA)-can be tuned with high sensitivity by selection of precursor carbide (composition, lattice type) and chlorination temperature. The optimum temperature is bounded from below by thermodynamics and kinetics of chlorination reactions and from above by graphitization, which decreases SSA and introduces H2-sorbing surfaces with binding energies too low to be useful. Intuitively, pores of different size and shape should not contribute equally to hydrogen storage. By correlating pore properties with 77 K H2 isotherms from a wide variety of CDCs, we experimentally confirm that gravimetric hydrogen storage capacity normalized to total pore volume is optimized in materials with primarily micropores ( approximately 1 nm) rather than mesopores. Thus, in agreement with theoretical predictions, a narrow size distribution of small pores is desirable for storing hydrogen, while large pores merely degrade the volumetric storage capacity.     

Pt-CeO2/SiO2催化剂用于室温湿空气中CO氧化反应

开发室温CO氧化催化剂的主要挑战是CO自中毒和慢的表面动力学,同时湿气的存在也可导致催化剂失活.本文开发了高活性CeO2促进的Pt基催化剂4%Pt-12%CeO2/SiO2,用于室温湿气(湿度10%?90%,25°C)中CO氧化反应,在低CO浓度(<500 ppm)和高CO浓度(>2500 ppm)时,CO转化率高于99%.优化了催化剂制备变量,如Pt和CeO2负载量、CeO2沉积方法、CeO2和Pt前驱体的干燥和焙烧条件.采用CO/H2化学吸附、O2-H2滴定、X射线衍射和BET比表面积测定表征了催化剂的表面特性,并将其与催化剂活性相关联.结果表明,CeO2沉积方法对催化剂活性影响显著,当用浸渍法沉积CeO2时,所得催化剂的反应速率(5.77μmol/g/s)比用沉积沉淀法(1.96μmol g?1 s?1)或CeO2嫁接法(1.31μmol g?1 s?1)制得催化剂的高3倍.O2-H2滴定结果表明,当用浸渍法沉积CeO2时,CeO2和Pt的紧密结合导致了催化剂的高活性.催化剂载体的选择也非常重要,硅胶负载的催化剂活性(5.77μmol g?1 s?1)是氧化铝负载的(1.05μmol g?1 s?1)5倍.当反应受内扩散控制时,催化剂载体的粒径和孔结构影响非常大.另外,CeO2和Pt前驱体的干燥和焙烧条件对催化剂活性的影响至关重要.当Pt和CeO2含量分别大于2.5和15 wt%时,所得催化剂在室温条件下活性高(TOF>0.02 s?1),稳定性好(反应15 h,CO转化率≥99%).     

A solid molecular basket sorbent for CO2 capture from gas streams with low CO2 concentration under ambient conditions

In this paper, a solid molecular basket sorbent, 50 wt% PEI/SBA-15, was studied for CO(2) capture from gas streams with low CO(2) concentration under ambient conditions. The sorbent was able to effectively and selectively capture CO(2) from a gas stream containing 1% CO(2) at 75 °C, with a breakthrough and saturation capacity of 63.1 and 66.7 mg g(-1), respectively, and a selectivity of 14 for CO(2)/CO and 185 for CO(2)/Ar. The sorption performance of the sorbent was influenced greatly by the operating temperature. The CO(2)-TPD study showed that the sorbent could be regenerated under mild conditions (50-110 °C) and was stable in the cyclic operations for at least 20 cycles. Furthermore, the possibility for CO(2) capture from air using the PEI/SBA-15 sorbent was studied by FTIR and proved by TPD. A capacity of 22.5 mg g(-1) was attained at 75 °C via a TPD method using a simulated air with 400 ppmv CO(2) in N(2).     

Defect and interface engineering for electrochemical nitrogen reduction reaction under ambient conditions

Electrochemical nitrogen reduction reaction(e-NRR)under ambient conditions is an emerging strategy to tackle the hydrogen-and energy-intensive operations for traditional Haber-Bosch process in industrial ammonia(NH₃)synthesis.However,the e-NRR performance is currently impeded by the inherent inertness of N₂ molecules,the extremely slow kinetics and the overwhelming competition from the hydrogen evolution reaction(HER),all of which cause unsatisfied yield and ammonia selectivity(Faradaic efficiency,FE).Defect and interface engineering are capable of achieving novel physical and chemical properties as well as superior synergistic effects for various electrocatalysts.In this review,we first provide a general introduction to the NRR mechanism.We then focus on the recent progress in defect and interface engineering and summarize how defect and interface can be rationally designed and functioned in NRR catalysts.Particularly,the origin of superior NRR catalytic activity by applying these approaches was discussed from both theoretical and experimental perspectives.Finally,the remaining challenges and future perspectives in this emerging area are highlighted.It is expected that this review will shed some light on designing NRR electrocatalysts with excellent activity,selectivity and stability.     

High-density storage of H2 in microporous crystalline silica at ambient conditions

Molecular hydrogen was encapsulated in the cages of clathrasil decadodecasil 3R (DD3R) during the hydrothermal synthesis of this microporous silicate. The crystalline structure of DD3R facilitates high-density hydrogen storage at ambient conditions. Prompt gamma activation analysis (PGAA) revealed that on average about one molecule of H2 is trapped in each (5(12)) cage of DD3R. The presence of molecular hydrogen inside the DD3R framework was confirmed by solid-state 1H NMR spectroscopy. Temperature-programmed decomposition (TPD) in combination with mass spectrometry showed that the encapsulated hydrogen is released upon decomposition of the clathrasil structure. This release can be promoted by the presence of water.     

A new approach towards tetrahedral imidazolate frameworks for high and selective CO2 uptake

Successful development of a new synthetic approach towards tetrahedral imidazolate frameworks (TIFs) via combining an auxiliary uninegative linker into the zinc-imidazolate tetrahedral assembly leads to new TIF materials (TIF-A1 to TIF-A3) with distinct structural topologies and high CO(2) uptake capacity.     

Noninvasive functionalization of polymers of intrinsic microporosity for enhanced CO(2) capture

Modifying sorbents for the purpose of improving carbon dioxide capture often results in the loss of surface area or accessible pores, or both. We report the first noninvasive functionalization of the polymers of intrinsic microporosity (PIMs) where inclusion of the amidoxime functionality in PIM-1 increases carbon dioxide capacity up to 17% and micropore surface area by 20% without losing its film forming ability.     

Salen–Mg-doped NH2–MIL-101(Cr) for effective CO2 adsorption under ambient conditions

A novel metal-doped metal–organic framework (MOF) was developed by incorporating salen–Mg into NH₂–MIL-101(Cr) structure under ambient conditions. The Schiff base complex was successfully prepared by condensing salicylaldehyde with a free amino group and then coordinating metal ions. Such a structure can endow the sample with higher CO₂ adsorption performance. At 0°C and 1 bar, the salen–Mg-modified sample achieves the maximum adsorption capacity of 2.18 mmol g⁻¹ for CO₂, which was 5.8% higher than the pristine salen–MOF under the same conditions. Notably, the Freundlich model indicates that the CO₂ adsorption process of all samples conforms to reversible adsorption. However, the correlation coefficients (R²) of the Mg-doped sample are lower than that of the pristine sample. Besides, the CO₂/N₂ adsorption selectivity and isosteric heat also show a similar trend. These results indicate that the salen–Mg can enhance the interaction between the material and CO₂ molecules.     

Silver-anchored porous aromatic framework for efficient conversion of propargylic alcohols with CO2 at ambient pressure

The conversion of propargylic alcohols and carbon dioxide (CO₂) into fine chemicals suffers from issues of harsh reaction conditions and difficult catalyst recovery. To achieve efficient CO₂ activation at low energy consumption, a silver-anchored porous aromatic framework catalyst Ag@PAF-DAB with high active phase density and CO₂ adsorption capacity was proposed. Since Ag@PAF-DAB has the dual functions of CO₂ capture and conversion, propargylic alcohols were completely converted into α-alkylidene cyclic carbonate or α?hydroxy ketone as high value-added product under atmospheric pressure (CO₂, 0.1 MPa) and low silver equivalent (0.5 mol%). Notably, Ag@PAF-DAB exhibited broad substrate diversity, high stability, and excellent reusability. By applying FTIR and GC, the key to green synthetic route of α?hydroxy ketone was confirmed to lie in the further hydration of α-alkylidene cyclic carbonate.     

Catalytic role of carbons in methane decomposition for CO- and CO2-free hydrogen generation

Decomposition of methane is an environmentally attractive approach to CO- and CO(2)-free hydrogen production. Using first principles calculations at the density functional theory level, our studies demonstrate that the defective carbons can be used as catalysts for methane decomposition, without the need for other catalysts, such as transition metals or oxides, and the catalytic sites can be regenerated by the deposition of carbon decomposed from methane, to make the hydrogen production a continuous process. Additionally, since no other gases are produced in the process, the cost of CO(2) sequestration and hydrogen purification from CO contamination will be dramatically reduced.     

DFT-based prediction of high-pressure H2 adsorption on porous carbons at ambient temperatures from low-pressure adsorption data measured at 77 K

Hydrogen adsorption isotherms were measured both at cryogenic temperatures below 1 atm and at ambient temperature at high pressures, up to 90 atm, on selected porous carbons with various pore structures. The nonlocal density functional theory (NLDFT) model was used to calculate the pore size distributions (PSDs) of the carbons, from H2 adsorption isotherms measured at 77 K, and then to predict H2 adsorption on these carbons at 87 and 298 K. An excellent agreement between the predicted and measured data was obtained. Prior to analyzing the porous carbons, the solid-fluid interaction parameters used in the NLDFT model were derived from H2 adsorption data measured at 77 K on nonporous carbon black. The results show that the NLDFT model with appropriate parameters may be a useful tool for optimizing carbon pore structures and designing adsorption systems for hydrogen storage applications.     

Tailoring pore properties of MCM-48 silica for selective adsorption of CO2

Four different types of amine-attached MCM-48 silicas were prepared and investigated for CO(2) separation from N(2). Monomeric and polymeric hindered and unhindered amines were attached to the pore surface of the MCM-48 silica and characterized with respect to their CO(2) sorption properties. The pore structures and amino group content in these modified silicas were investigated by XRD, FT-IR, TGA, N(2) adsorption/desorption at 77 K and CHN/Si analysis, which confirmed that in all cases the amino groups were attached to the pore surface of MCM-48 at 1.5-5.2 mmol/g. The N(2) adsorption/desorption analysis showed a considerable decrease of the pore volume and surface area for the MCM-48 silica containing a polymeric amine (e.g., polyethyleneimine). The CO(2) adsorption rates and capacities of the amine-attached MCM-48 samples were studied employing a sorption microbalance. The results obtained indicated that in addition to the concentration of surface-attached amino groups, specific interactions between CO(2) and the surface amino groups, and the resultant pore structure after amine group attachment have a significant impact on CO(2) adsorption properties of these promising adsorbent materials.     

Direct CO2 capture and conversion to fuels on magnesium nanoparticles under ambient conditions simply using water

Converting CO₂ directly from the air to fuel under ambient conditions is a huge challenge. Thus, there is an urgent need for CO₂ conversion protocols working at room temperature and atmospheric pressure, preferentially without any external energy input. Herein, we employ magnesium (nanoparticles and bulk), an inexpensive and the eighth-most abundant element, to convert CO₂ to methane, methanol and formic acid, using water as the sole hydrogen source. The conversion of CO₂ (pure, as well as directly from the air) took place within a few minutes at 300 K and 1 bar, and no external (thermal, photo, or electric) energy was required. Hydrogen was, however, the predominant product as the reaction of water with magnesium was favored over the reaction of CO₂ and water with magnesium. A unique cooperative action of Mg, basic magnesium carbonate, CO₂, and water enabled this CO₂ transformation. If any of the four components was missing, no CO₂ conversion took place. The reaction intermediates and the reaction pathway were identified by ¹³CO₂ isotopic labeling, powder X-ray diffraction (PXRD), nuclear magnetic resonance (NMR) and in situ attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), and rationalized by density-functional theory (DFT) calculations. During CO₂ conversion, Mg was converted to magnesium hydroxide and carbonate, which may be regenerated. Our low-temperature experiments also indicate the future prospect of using this CO₂-to-fuel conversion process on the surface of Mars, where CO₂, water (ice), and magnesium are abundant. Thus, even though the overall process is non-catalytic, it could serve as a step towards a sustainable CO₂ utilization strategy as well as potentially being a first step towards a magnesium-driven civilization on Mars.

We demonstrated the use of magnesium nanoparticles (and bulk) to convert CO₂ (pure & also from the air) to methane, methanol, formic acid and green cement without external energy within a few minutes, using only water as the sole hydrogen source.     

Tailoring the structural,magnetic and antimicrobial activity of AgCrO2 delafossite at high annealing temperature

In the present study, we prepared AgCrO₂ delafossite at high annealing temperature 800 °C by flash auto-combustion technique which is an easy and a low-cost method. The objective of this study was to tailor the structural, magnetic and antimicrobial study of AgCrO₂ delafossite at this high annealing temperature (800 °C) which can be used in the fascinating applications. The sample was examined using X-ray diffraction pattern to confirm its single-phase hexagonal structure. Moreover, the morphology was analyzed by the field-emission scanning electron microscopy to clarify that AgCrO₂ delafossite was in the nanoscale range. The energy-dispersive X-ray analysis was performed to show the composition of the sample. The room-temperature magnetic hysteresis loop assured that the sample had superparamagnetic behavior. The investigated sample AgCrO₂ delafossite can be considered to have a strong antibacterial activity against Gram-positive and Gram-negative bacteria. However, by studying the effect of AgCrO₂ delafossite against fungi microorganism, no activity was detected using AgCrO₂ delafossite. The promising application of this study is to add AgCrO₂ delafossite to various drugs as an antibacterial agent.