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  • Solution processable metal–organic frameworks for mixed matrix membranes using porous liquids

    Knebel, Alexander; Bavykina, Anastasiya; Datta, Shuvo Jit; Sundermann, Lion; Garzon Tovar, Luis Carlos; Lebedev, Yury; Durini, Sara; Ahmad, Rafia; Kozlov, Sergey; Shterk, Genrikh; Karunakaran, Madhavan; Carja, Ionela-Daniela; Simic, Dino; Weilert, Irina; Klüppel, Manfred; Giese, Ulrich; Cavallo, Luigi; Rueping, Magnus; Eddaoudi, Mohamed; Caro, Jürgen; Gascon, Jorge (Nature Materials, Springer Science and Business Media LLC, 2020-08-10) [Article]
    The combination of well-defined molecular cavities and chemical functionality makes crystalline porous solids attractive for a great number of technological applications, from catalysis to gas separation. However, in contrast to other widely applied synthetic solids such as polymers, the lack of processability of crystalline extended solids hampers their application. In this work, we demonstrate that metal-organic frameworks, a type of highly crystalline porous solid, can be made solution processable via outer surface functionalization using N-heterocyclic carbene ligands. Selective outer surface functionalization of relatively large nanoparticles (250 nm) of the well-known zeolitic imidazolate framework ZIF-67 allows for the stabilization of processable dispersions exhibiting permanent porosity. The resulting type III porous liquids can either be directly deployed as liquid adsorbents or be co-processed with state-of-the-art polymers to yield highly loaded mixed matrix membranes with excellent mechanical properties and an outstanding performance in the challenging separation of propylene from propane. We anticipate that this approach can be extended to other metal-organic frameworks and other applications.
  • Gas separation and water desalination performance of defect-free interfacially polymerized para-linked polyamide thin-film composite membranes

    Ali, Zain; Wang, Yingge; Ogieglo, Wojciech; Pacheco Oreamuno, Federico; Vovusha, Hakkim; Han, Yu; Pinnau, Ingo (Journal of Membrane Science, Elsevier BV, 2020-08-10) [Article]
    Introduction of interfacially polymerized (IP) polyamide thin-film composite (TFC) membranes in the 1980s revolutionized the reverse osmosis desalination industry. However, IP-derived TFCs have not achieved industrial success for gas separation applications due to the presence of membrane defects in their dry state. In this work, we report defect-free crosslinked polyamide thin-film composite membranes prepared from para-substituted aromatic and cycloaliphatic diamines, p-phenylenediamine (PPD) and piperazine (PIP), reacted with trimesoyl chloride (TMC). The key parameters in our modified IP process to mitigate defects are long reaction time (∼5 min) and high organic solution temperature (100 °C). The gas separation and desalination properties of the para-linked polyamide membranes were compared to previously reported polyamide TFCs made from meta-phenylenediamine (MPD) and TMC. The gas- and water permeances of the TFCs increased in the order: MPD-TMC < PPD-TMC < PIP-TMC, whereas gas-pair selectivities and salt rejections followed the opposite sequential trend: MPD-TMC > PPD-TMC ≥ PIP-TMC. Elimination of defects allowed exploitation of the ultra-selective nature of polyamide TFCs, specifically for hydrogen and helium separations. At 23 °C, PIP-TMC, PPD-TMC and MPD-TMC exhibited H2/CH4 selectivities of 312, 362 and 1290, respectively, with moderate H2 permeances of 37.4, 32.6 and 25.8 GPU (1 GPU = 10−6 cm3(STP) cm−2 s−1 cmHg−1). Furthermore, the TFCs demonstrated excellent performance for H2/CO2 separation with pure-gas selectivities of 10-14 at 23 °C. The strong size-sieving capability of the polyamide TFCs originated from tight interchain packing induced by strong hydrogen bonding. Wide-angle X-ray diffraction confirmed a dominant fraction of submicropores of less than ∼4 Å within PPD-TMC and PIP-TMC polyamide networks.
  • Spontaneous solar water splitting with decoupling of light absorption and electrocatalysis using silicon back-buried junction.

    Fu, Hui-Chun; Varadhan, Purushothaman; Lin, Chun-Ho; He, Jr-Hau (Nature communications, Springer Science and Business Media LLC, 2020-08-09) [Article]
    Converting sunlight into a storable form of energy by spontaneous water splitting is of great interest but the difficulty in simultaneous management of optical, electrical, and catalytic properties has limited the efficiency of photoelectrochemical (PEC) devices. Herein, we implemented a decoupling scheme of light harvesting and electrocatalysis by employing a back-buried junction (BBJ) PEC cell design, which enables >95% front side light-harvesting, whereas the electrochemical reaction in conjunction with carrier separation/transport/collection occurs on the back side of the PEC cell. The resultant silicon BBJ-PEC half-cell produces a current density of 40.51 mA cm-2 for hydrogen evolution by minimizing optical, electrical, and catalytic losses (as low as 6.11, 1.76, and 1.67 mA cm-2, respectively). Monolithic fabrication also enables three BBJ-PEC cells to be connected in series as a single module, enabling unassisted solar water-splitting with a solar-to-hydrogen conversion efficiency of 15.62% and a hydrogen generation rate of 240 μg cm-2 h-1.
  • [Pd(NHC)(μ-Cl)Cl]2: Versatile and Highly Reactive Complexes for Cross-Coupling Reactions that Avoid Formation of Inactive Pd(I) Off-Cycle Products.

    Zhou, Tongliang; Ma, Siyue; Nahra, Fady; Obled, Alan M C; Poater, Albert; Cavallo, Luigi; Cazin, Catherine S. J.; Nolan, Steven P; Szostak, Michal (iScience, Elsevier BV, 2020-08-08) [Article]
    The development of more reactive, general, easily accessible, and readily available Pd(II)-NHC precatalysts remains a key challenge in homogeneous catalysis. In this study, we establish air-stable NHC-Pd(II) chloro-dimers, [Pd(NHC)(μ-Cl)Cl]2, as the most reactive Pd(II)-NHC catalysts developed to date. Most crucially, compared with [Pd(NHC)(allyl)Cl] complexes, replacement of the allyl throw-away ligand with chloride allows for a more facile activation step, while effectively preventing the formation of off-cycle [Pd2(μ-allyl)(μ-Cl)(NHC)2] products. The utility is demonstrated via broad compatibility with amide cross-coupling, Suzuki cross-coupling, and the direct, late-stage functionalization of pharmaceuticals. Computational studies provide key insight into the NHC-Pd(II) chloro-dimer activation pathway. A facile synthesis of NHC-Pd(II) chloro-dimers in one-pot from NHC salts is reported. Considering the tremendous utility of Pd-catalyzed cross-coupling reactions and the overwhelming success of [Pd(NHC)(allyl)Cl] precatalysts, we believe that NHC-Pd(II) chloro-dimers, [Pd(NHC)(μ-Cl)Cl]2, should be considered as go-to precatalysts of choice in cross-coupling processes.
  • Electroactive biofilms on surface functionalized anodes: the anode respiring behavior of a novel electroactive bacterium, Desulfuromonas acetexigens

    Katuri, Krishna; Kamireddy, Sirisha; Kavanagh, Paul; Muhammad, Ali; Conghaile, Peter Ó; Kumar, Amit; Saikaly, Pascal; Leech, Dónal (Water Research, Elsevier BV, 2020-08-07) [Article]
    urface chemistry is known to influence the formation, composition, and electroactivity of electron-conducting biofilms. However, understanding of the evolution of microbial composition during biofilm development and its impact on the electrochemical response is limited. Here we present voltammetric, microscopic and microbial community analysis of biofilms formed under fixed applied potential for modified graphite electrodes during early (90 h) and mature (340 h) growth phases. Electrodes modified to introduce hydrophilic groups (-NH2, -COOH and -OH) enhance early-stage biofilm formation compared to unmodified or electrodes modified with hydrophobic groups (-C2H5). In addition, early-stage films formed on hydrophilic electrodes were dominated by the gram-negative sulfur-reducing bacterium Desulfuromonas acetexigens while Geobacter sp. dominated on -C2H5 and unmodified electrodes. As biofilms mature, current generation becomes similar, and D. acetexigens dominates in all biofilms irrespective of surface chemistry. Electrochemistry of pure culture D. acetexigens biofilms reveal that this microbe is capable of forming electroactive biofilms producing considerable current density of > 9 A/m2 in a short period of potential induced growth (∼19 h followed by inoculation) using acetate as an electron donor. The inability of D. acetexigens biofilms to use H2 as a sole source electron donor for current generation shows promise for maximizing H2 recovery in single-chambered microbial electrolysis cell systems treating wastewaters.

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