University of California

Exxonmobil Research and Engineering Company

Robert Boschgmbh

Exxonmobil Technology and Engineering Company

Jeffrey R Long

Christopher J Chang

Rebecca L Siegelman

Phillip J Milner

Simon Christopher Weston

Thomas M McDonald

Hemamala Indivari Karunadasa

Brian M Wiers

Jeffrey F Van Humbeck

Jeffrey D Martell

Joseph M Falkowski

Nitash Balsara

Marcin Majda

Sumin Lee

Eric D Bloch

Deanna M D'Alessandro

Matthew Kapelewski

Douglas A Reed

Gokhan Barin

John F Christensen

Hany Basam Eitouni

Sondra L Hellstrom

Zachary Pace Smith

Benjamin Keith Keitz

Rob Ameloot

Katherine Harry

Rajamani Krishna

Leslie Murray

David E Jaramillo

Miguel Carlos I Gonzalez

Stephen J Geier

Kristen Colwell

Michael Aubrey

Dianne J Xiao

David Abram

Rodolfo Torres

Jordan Axelson

Zoey R Herm

Yujie Sun

Dana J Levine

Jarad A Mason

Matthias Loipersberger

Jeffrey S Derrick

Martin Head-Gordon

Mercedes K Taylor

Miguel I Gonzalez

Julia Oktawiec

Adam Uliana

Eugene J Kim

Jordan C Axelson

Jonathan Bachman

Ether-thioether functionalized porous aromatic framework (PAF) polymers provide high selectivity for iron(II) and iron(III) adsorption in aqueous samples.

Iron detection and remediation with a functionalized porous polymer

An adsorption material is disclosed that comprises a metal-organic framework and a plurality of ligands. The metal-organic framework comprising a plurality of metal ions. Each respective ligand in the plurality of ligands is amine appended to a respective metal ion in the plurality of metal ions of the metal-organic framework. Each respective ligand in the plurality of ligands comprises a substituted 1,3-propanediamine. The adsorbent has a COadsorption capacity of greater than 2.50 mmol/g at 150 mbar COat 40° C. Moreover, the adsorbent is configured to regenerate at less than 120° C. An example ligand is diamine 2,2-dimethyl-1,3-propanediamine. An example of the metal-organic framework is Mg(dobpdc), where dobpdcis 4,4'-dioxidobiphenyl-3,3′-dicarboxylate. Example applications for the adsorption material are removal of carbon dioxide from flue gas and biogasses.

Amine-appended metal-organic frameworks exhibiting a new adsorption mechanism for carbon dioxide separations

A system and method for acid gas separations using porous frameworks of metal atoms coordinatively bound to polytopic linkers that are functionalized with basic nitrogen ligands that expose nitrogen atoms to the pore volumes forming adsorption sites. Adjacent basic nitrogen ligands on the metal-organic framework can form an ammonium from one ligand and a carbamate from the other. The formation of one ammonium carbamate pair influences the formation of ammonium carbamate on adjacent adsorption sites. Adsorption of acid gas at the adsorption sites form covalently linked aggregates of more than one ammonium carbamate ion pair. The acid gas adsorption isotherm can be tuned to match the step position with the partial pressure of acid gas in the gas mixture stream through manipulation of the metal-ligand bond strength by selection of the ligand, metal and polytopic linker materials.

Cooperative chemical adsorption of acid gases in functionalized metal-organic frameworks

The electrochemical carbon dioxide reduction reaction (CORR) provides opportunities to synthesize value-added products from this greenhouse gas in a sustainable manner. Efficient catalysts for this reaction are provided that selectively drive COreduction over the thermodynamic and kinetically competitive hydrogen evolution reaction (HER) in organic or aqueous electrolytes. The catalysts are metal-polypyridyl coordination complexes of a redox non-innocent terpyridine-based pentapyridine ligand and a first-row transition metal. The metal-ligand cooperativity in [Fe(tpyPY2Me)]drives the electrochemical reduction of COto CO at low overpotentials with high selectivity for CORR (&#x3e;90%).

Metal-ligand catalysts for selective promotion of electrochemical CORR

Primary, secondary (1&#xb0;,2&#xb0;) alkylethylenediamine- and alkylpropylenediamine-appended variants of metal-organic framework are provided for COcapture applications. Increasing the size of the alkyl group on the secondary amine enhances the stability to diamine volatilization from the metal sites. Two-step adsorption/desorption profiles are overcome by minimzing steric interactions between adjacent ammonium carbamate chains. For instance, the isoreticularly expanded framework Mg(dotpdc) (dotpdc=4,4&#x2033;-dioxido-[1,1':4&#x2032;,1&#x2033;-terphenyl]-3,3&#x2033;-dicarboxylate), yields diamine-appended adsorbents displaying a single COadsorption step. Further, use of the isomeric framework Mg-IRMOF-74-II or Mg(pc-dobpdc) (pc-dobpdc=3,3-dioxidobiphenyl-4,4-dicarboxylate, pc=para-carboxylate) also leads to a single COadsorption step with bulky diamines. By relieving steric interactions between adjacent ammonium carbamate chains, these frameworks enable step-shaped COadsorption, decreased water co-adsorption, and increased stability to diamine loss. Variants of Mg(dotpdc) and Mg(pc-dobpdc) functionalized with large diamines such as N-(n-heptyl)ethylenediamine have utility as adsorbents for carbon capture applications.

Overcoming two carbon dioxide adsorption steps in diamine-appended metal organic frameworks

An adsorbate-selective metal organic framework includes a transition metal; and a plurality of organic molecules coordinated to the transition metal so as to preserve open coordination sites for selectively adsorbing molecules that have low-lying &#x3c0;* orbitals. The transition metal has a lowest energy spin state in the presence of the selectively adsorbed molecules that are strongly bonding to the transition metal through &#x3c0;-donating interactions which is different than the lowest energy spin state in the absence of these adsorbed molecules. The transition metal has also a lowest energy spin state in the presence of non-selected molecules that are weakly bonding to the transition metal through &#x3c3;- and/or &#x3c0;-accepting and/or donating interactions.

Selective, adsorbate-induced spin state changes in transition metal-based metal-organic frameworks

An adsorption material is disclosed that comprises a metal-organic framework and a plurality of ligands. The metal-organic framework comprising a plurality of metal ions. Each respective ligand in the plurality of ligands is amine appended to a respective metal ion in the plurality of metal ions of the metal-organic framework. Each respective ligand in the plurality of ligands comprises a substituted 1,3-propanediamine. The adsorbent has a COadsorption capacity of greater than 2.50 mmol/g at 150 mbar COat 40&#xb0; C. Moreover, the adsorbent is configured to regenerate at less than 120&#xb0; C. An example ligand is diamine 2,2-dimethyl-1,3-propanediamine. An example of the metal-organic framework is Mg(dobpdc), where dobpdcis 4,4'-dioxidobiphenyl-3,3&#x2032;-dicarboxylate. Example applications for the adsorption material are removal of carbon dioxide from flue gas and biogasses.

A permanently porous vanadium(II)-containing metal-organic framework (MOF) with vanadium(II) centers and methods for synthesis of such MOF frameworks are provided. Methods for using such compounds to selectively react with Nover CHare provided. In the synthetic methods, a vanadium source, such as VY(tmeda), where Y is a halogen and tmeda is N,N,N',N&#x2032;-tetramethylethane-1,2-diamine and a H(ligand) are reacted in the presence of acid in a solvent at between 110&#xb0; C. and 130&#xb0; C. to form an intermediate product. The intermediate product is collected and washed with a washing agent, such as DMF and acetonitrile, and the vanadium(II) based MOF is activated by heating the washed intermediate product to at least 160&#xb0; C. under dynamic vacuum.

Vanadium metal-organic framework for selective adsorption

The disclosure provides for polymer membranes which comprise metal organic frameworks, methods of making therein, and methods of use thereof, including in gas separation.

Adsorption-enhanced and plasticization resistant composite membranes

Methods of synthesizing crystalline metal-organic frameworks (MOFs) comprising polytopic organic linkers and cations, where each linker is connected to two or more cations, are provided. In the disclosed methods, the linkers are reacted with a compound of formula MX, where M is cationic Be, Mg, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Cd, or Hf, X is anionic, n and m are integers. The reacting is buffered by a buffer devoid of metal coordinating functionality when the pKa of the anion is below a threshold related to the lowest pKa of the linker. The reacting is optionally not buffered when the pKa of the anion is at or above this threshold. The disclosed methods lead to product phase MOF in which crystal growth is controlled leading to control over molecular diffusion.

Metal-organic framework phase and crystallite shape control

Olsalazine (Holz), a prodrug of the anti-inflammatory 5-aminosalicylic acid, is used as a ligand to synthesize a suite of M(Holz) and M(olz) materials, where M is a dication (e.g. Mg, Ca, Sr, Fe, Co, Ni, Cu, Zn). A family of metal olsalazine coordination polymers, coordination solids, and metal organic frameworks are described, which include 1-, 2-, and 3-dimensional structures. The materials resist degradation at acidic pH and release olsalazine preferentially at neutral pH. The mesoporous M(olz) frameworks exhibit high surface areas with hexagonal pore apertures that are approximately 27 &#x212b; in diameter and contain coordinatively unsaturated metal sites. Biologically active molecules containing a Lewis-basic functional group can be grafted directly to the open metal sites of the frameworks. Dissolution of the frameworks under physiological conditions releases olsalazine (Holz) and the grafted molecules so that multiple therapeutic components can be delivered together at different rates.

Metal-olsalazine coordination polymers for medical applications

Polyamines with lengths carefully tailored to the framework dimensions are appended to metal-organic frameworks such as Mg(dobpdc) (dobpdc4-=4,4'-dioxidobiphenyl-3,3&#x2032;-dicarboxylate) with the desired loading of one polyamine per two metal sites. The polyamine-appended materials show step-shaped adsorption and desorption profiles due to a cooperative COadsorption/desorption mechanism. Several disclosed polyamine-appended materials exhibit strong ability to capture COfrom various compositions. Increased stability of amines in the framework has been achieved using high molecular weight polyamine molecules that coordinate multiple metal sites in the framework. The preparation of these adsorbents as well as their characterization are provided.

Polyamine-appended metal-organic frameworks for carbon dioxide separations

Primary, secondary (1&#xba;,2&#xba;) alkylethylenediamine- and alkylpropylenediamine-appended variants of metal-organic framework are provided for COcapture applications. Increasing the size of the alkyl group on the secondary amine enhances the stability to diamine volatilization from the metal sites. Two-step adsorption/desorption profiles are overcome by minimizing steric interactions between adjacent ammonium carbamate chains. For instance, the isoreticularly expanded framework Mg(dotpdc) (dotpdc=4,4&#x2033;-dioxido-[1,1':4&#x2032;,1&#x2033;-terphenyl]-3,3&#x2033;-dicarboxylate), yields diamine-appended adsorbents displaying a single COadsorption step. Further, use of the isomeric framework Mg-IRMOF-74-II or Mg(pc-dobpdc) (pc-dobpdc=3,3-dioxidobiphenyl-4,4-dicarboxylate, pc=para-carboxylate) also leads to a single COadsorption step with bulky diamines. By relieving steric interactions between adjacent ammonium carbamate chains, these frameworks enable step-shaped COadsorption, decreased water co-adsorption, and increased stability to diamine loss. Variants of Mg(dotpdc) and Mg(pc-dobpdc) functionalized with large diamines such as N-(n-heptyl)ethylenediamine have utility as adsorbents for carbon capture applications.

Overcoming two carbon dioxide adsorption steps in diamine-appended metal-organic frameworks

Solid electrolytes have a favorable combination of properties such as high conductivity, high transference number, optimum processability, and low brittleness. A composite electrolyte includes some amount of a class of network polymer electrolytes with high transference number and high room temperature conductivity, and an additional polymeric component to contribute mechanical integrity and/or processability. The solid electrolytes can include a network polymer having linked nodes composed of a tetrahedral arylborate composition and a linear polymer combined with the network polymer as a composite. The solid electrolytes can be used in thin films and in solid-state batteries.

Batteries with polymer electrolyte composites based on tetrahedral arylborate nodes

Achieving the selective and reversible adsorption of COfrom humid, low partial pressures streams such as the flue gas resulting from the combustion of natural gas in combined cycle power plants (4% CO) is challenging due to the need for high thermal, oxidative, and hydrolytic stability as well as moderate regeneration conditions to reduce the energy of adsorption/desorption cycling. Appending cyclic primary, secondary diamines, exemplified by 2-(aminomethyl)piperidine (2-ampd), to the metal-organic frameworks Mg(dobpdc) (dobpdc=4,4-dioxidobiphenyl-3,3-dicarboxylate), Mg(dotpdc) (dotpdc=4,4&#x2033;-dioxido-[1,1':4&#x2032;,1&#x2033;-terphenyl]-3,3&#x2033;-dicarboxylate) or Mg(pc-dobpdc) (pc-dobpdc=dioxidobiphenyl-4,4&#x2032;-dicarboxylate) produces adsorbents of the classes EMM-44, EMM-45, and EMM-46, respectively, that display step-shaped adsorption of COat the partial pressures required for 90% capture from natural gas flue gas at temperatures up to or exceeding 60&#xb0; C. Using a cyclic diamine in place of a diamine functionalized with bulky alkyl groups enables fast adsorption/desorption kinetics with sharp COadsorption and desorption steps.

Metal-organic frameworks appended with cyclic diamines for carbon dioxide capture

Growing community of inventors

Oakland, CA, United States of America

Jeffrey R Long