Fine pore engineering in a series of isoreticular metal-organic frameworks for efficient C2H2/CO2 separation

The separation of C2H2/CO2 is not only industrially important for acetylene purification but also scientifically challenging owing to their high similarities in physical properties and molecular sizes. Ultramicroporous metal-organic frameworks (MOFs) can exhibit a pore confinement effect to differentiate gas molecules of similar size. Herein, we report the fine-tuning of pore sizes in sub-nanometer scale on a series of isoreticular MOFs that can realize highly efficient C2H2/CO2 separation. The subtle structural differences lead to remarkable adsorption performances enhancement. Among four MOF analogs, by integrating appropriate pore size and specific binding sites, [Cu(dps)2(SiF6)] (SIFSIX-dps-Cu, SIFSIX = SiF62-, dps = 4.4’-dipyridylsulfide, also termed as NCU-100) exhibits the highest C2H2 uptake capacity and C2H2/CO2 selectivity. At room temperature, the pore space of SIFSIX-dps-Cu significantly inhibits CO2 molecules but takes up a large amount of C2H2 (4.57 mmol g−1), resulting in a high IAST selectivity of 1787 for C2H2/CO2 separation. The multiple host-guest interactions for C2H2 in both inter- and intralayer cavities are further revealed by dispersion-corrected density functional theory and grand canonical Monte Carlo simulations. Dynamic breakthrough experiments show a clean C2H2/CO2 separation with a high C2H2 working capacity of 2.48 mmol g−1.

A quantitive microscale dynamic column breakthrough apparatus for measurement of unary and binary adsorption equilibrium on milligram quantities of adsorbent

A microscale dynamic column breakthrough (μDCB) apparatus with the ability to measure unary and binary adsorption equilibrium on a milligram-scale quantity of adsorbent is described. The μDCB is a low cost system that can be constructed through minor modifications of a commercial gas chromatograph and uses a thermal conductivity detector. The small scale of the apparatus allows for the rapid collection of dynamic column breakthrough experiments. The mass balances for adsorption and desorption experiments were derived along with a description of the blank. The μDCB apparatus was tested with 238.9 mg of zeolite 13X and 180.2 mg of activated carbon with single-component N2/He and CH4/He adsorption and desorption measurements. The measured equilibrium data agreed well with volumetrically collected data. These measurements are both accurate and precise. Multicomponent adsorption was also studied on zeolite 13X and activated carbon for CH4/N2 and CO2/CH4 mixtures. This data was compared with ideal and adsorbed solution theory, extended dual-site Langmuir calculations and the literature.

Impact of Integrase Sequences From HIV-1 Subtypes A6/A1 on the In Vitro Potency of Cabotegravir or Rilpivirine

The FLAIR study demonstrated noninferiority of monthly long-acting cabotegravir + rilpivirine vs daily oral dolutegravir/abacavir/lamivudine for maintaining virologic suppression. Three participants who received long-acting therapy had confirmed virologic failure (CVF) at Week 48, and all had HIV-1 that was originally classified as subtype A1 and contained the baseline integrase polymorphism L74I; updated classification algorithms reclassified all 3 as HIV-1 subtype A6. Retrospectively, the impact of L74I on in vitro sensitivity and durability of response to cabotegravir in HIV-1 subtype B and A6 backgrounds was studied. Site-directed L74I and mutations observed in participants with CVF were generated in HIV-1 subtype B and a consensus integrase derived from 3 subtype A6 CVF baseline sequences. Rilpivirine susceptibility was assessed in HIV-1 subtype B and A1 containing reverse transcriptase mutations observed in participants with CVF. HIV-1 subtype B L74I and L74I/G140R mutants and HIV-1 subtype A6 I74L and I74/G140R mutants remained susceptible to cabotegravir; L74I/Q148R double mutants exhibited reduced susceptibility in HIV-1 subtypes B and A6 (half maximal effective capacity fold change, 4.4 and 4.1, respectively). Reduced rilpivirine susceptibility was observed across HIV-1 subtypes B and A1 with resistance-associated mutations K101E or E138K (half maximal effective capacity fold change, 2.21 to 3.09). In cabotegravir breakthrough experiments, time to breakthrough was similar between L74 and I74 viruses across HIV-1 subtypes B and A6; Q148R was selected at low cabotegravir concentrations. Therefore, the L74I integrase polymorphism did not differentially impact in vitro sensitivity to cabotegravir across HIV-1 subtype B and A6 integrase genes (ClinicalTrials.gov identifier: NCT02938520).

Alternative Materials for the Enrichment of Biogas with Methane

Carbonaceous adsorbents have been pointed out as promising adsorbents for the recovery of methane from its mixture with carbon dioxide, including biogas. This is because of the fact that CO2 is more strongly adsorbed and also diffuses faster compared to methane in these materials. Therefore, the present study aimed to test alternative carbonaceous materials for the gas separation process with the purpose of enriching biogas in biomethane and to compare them with the commercial one. Among them was coconut shell activated carbon (AC) as the adsorbent derived from bio-waste, rubber tire pyrolysis char (RPC) as a by-product of waste utilization technology, and carbon molecular sieve (CMS) as the commercial material. The breakthrough experiments were conducted using two mixtures, a methane-rich mixture (consisting of 75% CH4 and 25% CO2) and a carbon dioxide-rich mixture (containing 25% CH4 and 75% CO2). This investigation showed that the AC sample would be a better candidate material for the CH4/CO2 separation using a fixed-bed adsorption column than the commercial CMS sample. It is worth mentioning that due to its poorly developed micropore structure, the RPC sample exhibited limited adsorption capacity for both compounds, particularly for CO2. However, it was observed that for the methane-rich mixture, it was possible to obtain an instantaneous concentration of around 93% CH4. This indicates that there is still much potential for the use of the RPC, but this raw material needs further treatment. The Yoon–Nelson model was used to predict breakthrough curves for the experimental data. The results show that the data for the AC were best fitted with this model.

One-step ethylene production from a four-component gas mixture by a single physisorbent

One-step adsorptive purification of ethylene (C2H4) from four-component gas mixtures comprising acetylene (C2H2), ethylene (C2H4), ethane (C2H6) and carbon dioxide (CO2) is an unmet challenge in the area of commodity purification. Herein, we report that the ultramicroporous sorbent Zn-atz-oba (H2oba = 4,4-dicarboxyl diphenyl ether; Hatz = 3-amino-1,2,4-triazole) enables selective adsorption of C2H2, C2H6 and CO2 over C2H4 thanks to the binding sites that lie in its undulating pores. Molecular simulations provide insight into the binding sites in Zn-atz-oba that are responsible for coadsorption of C2H2, C2H6 and CO2 over C2H4. Dynamic breakthrough experiments demonstrate that the selective binding exhibited by Zn-atz-oba can produce polymer-grade purity (>99.95%) C2H4 from binary (1:1 for C2H4/C2H6), ternary (1:1:1 for C2H2/C2H4/C2H6) and quaternary (1:1:1:1 for C2H2/C2H4/C2H6/CO2) gas mixtures in a single step.

Efficient propyne/propadiene separation by microporous crystalline physiadsorbents

Selective separation of propyne/propadiene mixture to obtain pure propadiene (allene), an essential feedstock for organic synthesis, remains an unsolved challenge in the petrochemical industry, thanks mainly to their similar physicochemical properties. We herein introduce a convenient and energy-efficient physisorptive approach to achieve propyne/propadiene separation using microporous metal-organic frameworks (MOFs). Specifically, HKUST-1, one of the most widely studied high surface area MOFs that is available commercially, is found to exhibit benchmark performance (propadiene production up to 69.6 cm3/g, purity > 99.5%) as verified by dynamic breakthrough experiments. Experimental and modeling studies provide insight into the performance of HKUST-1 and indicate that it can be attributed to a synergy between thermodynamics and kinetics that arises from abundant open metal sites and cage-based molecular traps in HKUST-1.

Th-MOF showing six-fold imide-sealed pockets for middle-size-separation of propane from nature gas

Separation of propane from nature gas is of great importance to industry. However, in light of size-based separation, there still lacks effective method to directly separate propane from nature gas, due to the comparable physical properties for these light alkanes (C1-C4) and the middle size of propane. In this work, we found that a new Th-MOF could be an ideal solution for this issue. The Th-MOF takes UiO-66-type structure, but with the pocket sealed by six-fold imide groups; this not only precisely reduces the size of pocket to exactly match propane, but also enhances the host-guest interactions through multiple supramolecular interactions. As a result, highly selective adsorption of propane over methane, ethane, and butane was observed, implying unique middle-size separation. The actual separation was confirmed by breakthrough experiments, and it is found that both relatively smaller molecules (methane and ethane) and relatively bigger molecules (butane) break through the Th-MOF column within 10 min/g, whereas propane with middle size can maintain very long retention time up to 80 min/g, strongly suggesting middle-size separation and its superior application in direct separation of propane from nature gas. The separation mechanism, as unveiled by both theoretical calculation and comparative experiments, is due to the six-fold imide-sealed pockets that could effectively distinguish propane from other light alkanes through both size effect and host-guest interactions.

3D Printed PEI Containing Adsorbents Supported by Carbon Nanostructures for Post-combustion Carbon Capture From Biomass Fired Power Plants

Processes that utilize solid adsorbents to capture CO2 are promising alternatives to state-of-art Amine based technologies for capturing CO2 from large point sources. Although the energy needs of solid sorbent-based processes are low, the process footprint and consequently the capital cost connected to its implementation can be large due to the relatively long cycle times needed to get the required purity and recovery of the CO2 product. To overcome this challenge, processes having structured adsorbents like laminates, monoliths etc. are needed due to their low pressure drop and better mass transfer characteristics. The aim of this multiscale study is to evaluate the process-based performance of a 3D printed sorbent containing polyethyleneimine (PEI) and multiwalled carbon nanotubes (MWCNT) for capturing CO2 from a biomass fired power plant flue gas. A 6-step vacuum swing adsorption (VSA) cycle was simulated and optimized using equilibrium and kinetics data obtained from volumetry and breakthrough experiments. The optimization study showed that it was possible to achieve purity values >95% and recovery values >90% from dry CO2 feed streams containing 10 and 15% CO2 respectively. The minimum specific energy values were 0.94 and 0.6 MJ/kg and maximum productivity values were 0.8 and 2.2 mol/m3 ads s, respectively, for the two scenarios.

Gram-Scale Synthesis of an Ultrastable Microporous Metal-Organic Framework for Efficient Adsorptive Separation of C2H2/CO2 and C2H2/CH4

A highly water and thermally stable metal-organic framework (MOF) Zn2(Pydc)(Ata)2 (1, H2Pydc = 3,5-pyridinedicarboxylic acid; HAta = 3-amino-1,2,4-triazole) was synthesized on a large scale using inexpensive commercially available ligands for efficient separation of C2H2 from CH4 and CO2. Compound 1 could take up 47.2 mL/g of C2H2 under ambient conditions but only 33.0 mL/g of CO2 and 19.1 mL/g of CH4. The calculated ideal absorbed solution theory (IAST) selectivities for equimolar C2H2/CO2 and C2H2/CH4 were 5.1 and 21.5, respectively, comparable to those many popular MOFs. The Qst values for C2H2, CO2, and CH4 at a near-zero loading in 1 were 43.1, 32.1, and 22.5 kJ mol−1, respectively. The practical separation performance for C2H2/CO2 mixtures was further confirmed by column breakthrough experiments.

Graduate School

This chapter relates how Esther Zimmer began working in bacteriology. At the beginning of September 1944, twenty-one-year old Esther Zimmer set off on a solitary four-day train journey to Palo Alto, California. Soon after arriving she met Edward Tatum, who was so impressed with her understanding of genetics that he invited her to be his teaching assistant in the graduate course in genetics. During the summer between her first and second years in graduate school, Zimmer took two courses in bacteriology taught by Cornelius van Niel. His bacteriology courses inspired a generation of molecular biologists and energized Zimmer’s engagement with bacteria, the model organisms that she would study for the rest of her scientific career. Back at Palo Alto, during the fall of 1945, she prepared the mutant bacterial strains of E. coli K-12 that Joshua Lederberg would use for his breakthrough experiments in bacterial conjugation.