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1. Carbon Molecular Sieve-derived POC/Mixed-Matrix Membranes for Gas Separation

   kowey, Isha ; Rownaghi, Ali ( May 2023 , North American Membrane Society 2023)

   Membrane-based separations offer the potential for the lowest energy demand requirements of all separation options. Among all nanoporous membranes, the carbon molecular sieves (CMS), metal-organic frameworks (MOFs), and mixed-matrix membranes (MMMs) with angstrom level molecular discrimination properties makes them appealing for separating a wide spectrum of gas-pairs. Here we present results of gas selectivity and diffusion of different gases (C2H6, C2H4, C3H8, C3H6, H2, N2, CO2, and CH4) in porous organic cages (POCs) incorporated into fluorinated copolyimides polymers (FCPs). The FCPs were synthesized by the iridization reaction of fluorinated dianhydrides, nonfluorinated dianhydride, and nonfluorinated diamine. Asymmetric hollow fiber membranes formed by the dry-jet/wet-quench spinning process. Once fresh FCP fibers were synthesized, they were crosslinked with POCs, vacuum dried at 90 °C. We investigated the uptake, gas selectivity and diffusion of different gases (C2H6, C2H4, C3H8, C3H6, H2, N2, CO2, and CH4) over synthesized POC-mixed matrixed membranes (POC-MMM) at 25 °C and pressures up to 1 bar. At 1 bar and 25 °C, C2H6, C2H4, C3H8, C3H6 adsorption capacities reached to 42.61, 2.56, 2.77 and 2.65 mmol/g over POC-MMM, respectively, while CO2, CH4, CO, N2 and H2 adsorption capacities of 1.48, 0.84, 0.33, 0.11, and 0.068 mmol/g, respectively. Furthermore, stable CMS membrane were formed by pyrolysis of POC-MMMs under an inert argon atmosphere at 1 atm. To test the gas transport properties of CMS-derived POC/MMM, a lab-scale hollow fiber module with two-five fibers was constructed. The results of longer-term operation of synthesized CMS membrane that was continuously operated for 264 h (10 days) with an equimolar binary H2/CO2, CH4/CO2 and C3H6/C3H8 feed at 25°C and 1 bar feed pressure. The modification yielded promising results in the reduction of physical aging of CMS membranes. 

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2. Electrocatalytic Conversion of Furanic Compounds for Production of Valuable Chemicals

   Li, Wenzhen ; Chadderdon, Xiaotong ; Chadderdon, David ; Liu, Hengzhou ( August 2021 , 72nd International Society of Electrochemistry Meeting)

   Biomass is abundant, inexpensive and renewable, therefore, it is highly expected to play a significant role in our future energy and chemical landscapes. The US DOE has identified furanic compounds (furfural and 5-(hydroxymethyl)furfural (HMF)) as the top platform building-block chemicals that can be readily derived from biomass sources [1]. Electrocatalytic conversion of these furanic compounds is an emerging route for the sustainable production of valuable chemicals [2, 3]. In my presentation, I will first present our recent mechanistic study of electrochemical reduction of furfural through a combination of voltammetry, preparative electrolysis, thiol-electrode modifications, and kinetic isotope studies [4]. It is demonstrated that two distinct mechanisms are operable on metallic Cu electrodes in acidic electrolytes: (i) electrocatalytic hydrogenation (ECH) and (ii) direct electroreduction. The contributions of each mechanism to the observed product distribution are clarified by evaluating the requirement for direct chemical interactions with the electrode surface and the role of adsorbed hydrogen. Further analysis reveals that hydrogenation and hydrogenolysis products are generated by parallel ECH pathways. Understanding the underlying mechanisms enables the manipulation of furfural reduction by rationally tuning the electrode potential, electrolyte pH, and furfural concentration to promote selective formation of important bio-based polymer precursors and fuels. Next, I will present electrocatalytic conversion of HMF to two biobased monomers in an H-type electrochemical cell [5]. HMF reduction (hydrogenation) to 2,5-bis(hydroxymethyl)furan (BHMF) was achieved under mild electrolyte conditions and ambient temperature using a Ag/C cathode. Meanwhile, HMF oxidation to 2,5-furandicarboxylic acid (FDCA) with ~100% efficiency was facilitated under the same conditions by a homogeneous nitroxyl radical redox mediator, together with an inexpensive carbon felt anode. The selectivity and efficiency for Ag-catalyzed BHMF formation were sensitive to cathode potential, owing to competition from HMF hydrodimerization reactions and water reduction (hydrogen evolution). Moreover, the carbon support of Ag/C was active for HMF reduction and contributed to undesired dimer/oligomer formation at strongly cathodic potentials. As a result, high BHMF selectivity and efficiency were only achieved within a narrow potential range near –1.3 V. Fortunately, the selectivity of redox-mediated HMF oxidation was insensitive to anode potential, thus allowing HMF hydrogenation and oxidation half reactions to be performed together in a single cathode-potential-controlled cell. Electrocatalytic HMF conversion in a paired cell achieved high molar yields of BHMF and FDCA, and nearly doubled electron efficiency compared to the unpaired cell. Finally, I will briefly introduce our recent work on the development of a three-electrode flow cell with an oxide-derived Ag (OD-Ag) cathode and catbon felt anode for paring elecatalytic oxidation and reduction of HMF. The flow cell has a remarkable cell voltage reduction from ~7.5 V to ~2.0 V by transferring the electrolysis from the H-type cell to the flow cell [6]. This represents a more than fourfold increase in the energy efficiency at the 10 mA operation. A combined faradaic efficiency of 163% was obtained to BHMF and FDCA. Alternatively, the anodic hydrogen oxidation reaction on platinum further reduced the cell voltage to only ~0.85 V at 10 mA operation. These paired processes have shown potential for integrating renewable electricity and carbon for distributed chemical manufacturing in the future. 

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3. Cobalt telluride electrocatalyst for selective electroreduction of CO2 to value-added chemicals

   https://doi.org/10.1007/s40243-022-00211-6  

   Saxena, Apurv ; Singh, Harish ; Nath, Manashi ( July 2022 , Materials for Renewable and Sustainable Energy)

   Recent emphasis on carbon dioxide utilization has necessitated the exploration of different catalyst compositions other than copper-based systems that can significantly improve the activity and selectivity towards specific CO₂ reduction products at low applied potential. In this study, a binary CoTe has been reported as an efficient electrocatalyst for CO₂reduction in aqueous medium under ambient conditions at neutral pH. CoTe showed high Faradaic efficiency and selectivity of 86.83 and 75%, respectively, for acetic acid at very low potential of − 0.25 V vs RHE. More intriguingly, C1 products like formic acid was formed preferentially at slightly higher applied potential achieving high formation rate of 547.24 μmol cm⁻² h⁻¹ at − 1.1 V vs RHE. CoTe showed better CO2RR activity when compared with Co₃O₄, which can be attributed to the enhanced electrochemical activity of the catalytically active transition metal center as well as improved intermediate adsorption on the catalyst surface. While reduced anion electronegativity and improved lattice covalency in tellurides enhance the electrochemical activity of Co, high d-electron density improves the intermediate CO adsorption on the catalyst site leading to CO₂reduction at lower applied potential and high selectivity for C₂products. CoTe also shows stable CO2RR catalytic activity for 50 h and low Tafel slope (50.3 mV dec^–1) indicating faster reaction kinetics and robust functionality. Selective formation of value-added C₂products with low energy expense can make these catalysts potentially viable for integration with other CO₂capture technologies thereby, helping to close the carbon loop.

    

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4. Reaction Mechanism Underlying Pd(II)-Catalyzed Oxidative Coupling of Ethylene and Benzene to Form Styrene: Identification of a Cyclic Mono-Pd II Bis-Cu II Complex as the Active Catalyst

   https://doi.org/10.1021/acs.organomet.2c00183  

   Musgrave, Charles B. ; Bennett, Marc T. ; Ellena, Jeffrey F. ; Dickie, Diane A. ; Gunnoe, T. Brent ; Goddard, William A. ( July 2022 , Organometallics)

   A recent advance in the synthesis of alkenylated arenes was the demonstration that the Pd(OAc)2 catalyst precursor gives >95% selectivity toward styrene from ethylene and benzene under optimized conditions using excess Cu(II) carboxylate as the in situ oxidant [ Organometallics 2019, 38(19), 3532−3541]. To understand the mechanism underlying this catalysis, we applied density functional theory (DFT) calculations in combination with experimental studies. From DFT calculations, we determined the lowest-energy multimetallic Pd and Pd–Cu mixed metal species as possible catalyst precursors. From the various structures, we determined the cyclic heterotrinuclear complex PdCu2(μ-OAc)6 to be the global minimum in Gibbs free energy under conditions of excess Cu(II). For cyclic PdCu2(μ-OAc)6 and the parent [Pd(μ-OAc)2]3, we evaluated the barriers for benzene C–H activation through concerted metalation deprotonation (CMD). The PdCu2(μ-OAc)6 cyclic trimer leads to a CMD barrier of 33.5 kcal/mol, while the [Pd(μ-OAc)2]3 species leads to a larger CMD barrier at >35 kcal/mol. This decrease in the CMD barrier arises from the insertion of Cu(II) into the trimetallic species. Because cyclic PdCu2(μ-OAc)6 is likely the predominant species under experimental conditions (the Cu to Pd ratio is 480:1 at the start of catalysis) with a predicted CMD barrier within the range of the experimentally determined activation barrier, we propose that cyclic PdCu2(μ-OAc)6 is the Pd species responsible for catalysis and report a full reaction mechanism based on DFT calculations. For catalytic conversion of benzene and ethylene to styrene at 120 °C using Pd(OAc)2 as the catalyst precursor and Cu(OPiv)2 (OPiv = pivalate) as the oxidant, an induction period of ∼1 h was observed, followed by catalysis with a turnover frequency of ∼2.3 × 10–3 s–1. In situ1H NMR spectroscopy experiments indicate that during the induction period, Pd(OAc)2 is likely converted to cyclic PdCu2(η2-C2H4)3(μ-OPiv)6, which is consistent with the calculations and consistent with the proposal that the active catalyst is the ethylene-coordinated heterotrinuclear complex cyclic PdCu2(η2-C2H4)3(μ-OPiv)6. 

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5. Cold plasma-Metal Organic Framework (MOF)-177 breathable system for atmospheric remediation

   https://doi.org/https://doi.org/10.1016/j.jcou.2021.101642  

   Fnu Gorky ; Apolo Nambo ; Maria L. Carreon ( July 2021 , Journal of CO2 utilization)

   Non-thermal plasma Methane capture Carbon dioxide capture Metal organic framework Methanol synthesis Atmospheric remediation 1. Introduction The stabilization of CO2 and CH4 concentrations in the air to control global warming is accelerating. There are continued efforts to develop and optimize different technologies for capture and sequestration of these greenhouse gases from industrial emission sites. From these gases, CH4 is the most dominant anthropogenic greenhouse gas (after CO2). Methane can react with nitrogen oxides leading to tropospheric ozone pollution and posses a higher global warming potential (GWP) than CO2. It is 84 times more potent than CO2 over the first 20 years after release and ~28 times more potent after a century. Methane concentrations could be restored to preindustrial levels by removing ~3.2 of the 5.3 Gt of CH4 currently in the atmosphere [1]. Rather than capturing and storing the methane, CH4 could be oxidized to CO2, through the ther- modynamically favorable reaction: CH4 + 2O2 → CO2 + 2H2O; ΔHrx = –803 kJ mol–1. With the possible production of valuable condensates such as form- aldehyde and methanol when employing different reaction conditions (i. e., gas ratio, oxidant type, temperature) and rational selected catalysts. The large activation barrier associated with splitting methane’s C– H * Corresponding author. E-mail address: Maria.CarreonGarciduenas@sdsmt.edu (M.L. Carreon). https://doi.org/10.1016/j.jcou.2021.101642 The direct capture of CO2 and CH4 from the atmosphere to stabilize the concentrations in the air to control global warming is accelerating. There are continued efforts to develop and optimize different technologies for capture and sequestration of these greenhouse gases from industrial emission sites. In this work we employed MOF-177 as an efficient CO2 and CH4 adsorbent at standard temperature and pressure conditions. We demonstrated the possibility of desorbing the gases under study when employing gentle plasma pulses of He. Moreover, we per- formed the synthesis of methanol from CH4 using O2 and CO2 as oxidants respectively in the presence of MOF- 177. We observed the highest conversion for the CH4 + O2 system when employing the MOF-177 at (5:1) (CH4: O2) flow ratio of 23.5 % and methanol selectivity of 17.65 %. While the best performance for the CH4 + CO2 system at the same conditions i.e., (5:1) (CH4: O2) flow ratio was 18.4 % for the methane conversion and 11.68 % for the selectivity towards methanol. We expect this preliminary understanding of the adsorption-reaction system under non-thermal plasma environment can lead to future atmospheric remediation technologies. 

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