Patent Application
20240309023
The present disclosure relates generally to the fields of chemistry and materials science. More particularly, it concerns molecular sorbents, methods of preparation thereof, compositions thereof and methods of use thereof, including separating gas molecules, such as ethylene, ethane, propylene, and propane.
Ethylene, the largest-volume organic product of the chemical industry, is produced mainly by the steam-cracking of petroleum feedstocks. This process results in a mixture of gaseous hydrocarbons that includes ethylene (C2H4) and ethane (C2H6). Industrial purification of ethylene from ethane is achieved by energy consuming, cryogenic distillation, which requires distillation columns with over 100 trays operating at temperatures around −25° C. and pressures >2000 kPa due to similarities in volatility (Sholl David and Lively Ryan et al., 2016; Chu et al., 2016). There have been extensive research endeavours to pursue materials for the cost-and energy-efficient separation of ethylene purification over the past half-decade but without significant progress. The emergence of porous metal-organic framework materials (MOFs) has primarily provided a promising option for this industrial gas separations given the fact that the pores of MOFs can be readily tuned for the sieving separations and functionalized for the specific recognition of one gas molecule over another one (Li et al., 2019; Lin et al., 2020). In fact, the inventors and other groups have successfully targeted several high-performance MOF materials for ethylene purification over the past several years (Bloch et al., 2012; He et al., 2012; Yang et al., 2015; Li et al., 2014; Aguado et al., 2012; Bereciartua et al., 2017; Li et al., 2018; Lin et al., 2018). Previous studies on the ultramicroporous metal-organic framework [Ca(C4O4)(H2O)] (UTSA-280) have shown this MOF to be selective for ethylene separation (Lin et al., Nat. Mater., 17(12):1128, 2018 and WO 2019/183635, both of which are incorporated by reference herein in their entireties).
Ethylene is also a plant hormone with many roles in growth and development including seed germination, fruit ripening, and senescence (Binder, 2020). Studies on ethylene receptor ETR1 indicate that copper is the cofactor in this protein, which binds ethylene quite tightly (Kd=2.4×10−9 M and a half-life for ethylene dissociation of 12.5 h) (Rodriguez et al., 1999; Schaller et al., 1995; Schott-Verdugo et al., 2019). Poly(pyrazolyl)borates, often referred to as scorpionates (Trofimenko et al., 1993), are a useful family of ligands for many applications including modelling ethylene receptor site of plants and obtaining isolable copper-ethylene complexes such as the tris(pyrazolyl)borate [(CH3)2Tp]Cu(C2H4)(1) (Thompson et al., 1983; Dias et al., 2008). In contrast to most copper(I) ethylene complexes which are quite air sensitive and labile (Munakata et al., 1986; Straub et al., 1999), the fluorinated analogue, [(CF3)2Tp]Cu(C2H4) (2) is a thermally stable solid and quite resistant to O2, and the loss of coordinated ethylene (Dias et al., 2002). Considering the current interest in non-porous materials that can facilitate ethylene-ethane separation without the need for cryogenic distillation (Parasar et al., 2020; Jayaratna et al., 2018; Cowan et al., 2015), it would be desirable to develop molecules that bind ethylene.
Given the usefulness of materials that can effectively separate industrial feedstocks, such as ethylene from ethane, or propylene from propane, materials that can achieve these separations are of great importance, including methods and processes to fabricate these materials.
In some aspects, the present disclosure provides new molecular sorbents, compositions thereof, methods of manufacturing these, and methods of use thereof. In one aspect, the present disclosure provides a compound of the formula:
wherein:
In some embodiments, the compound is further defined as:
wherein:
In some embodiments, the compound is further defined as:
wherein:
In some embodiments, R4 is substituted alkyl(C≤12). In some embodiments, R4 is substituted alkyl(C≤6). In some embodiments, R4 is haloalkyl(C≤6). In some embodiments, R4 is trifluoromethyl.
In some embodiments, R4′ is substituted alkyl(C≤12). In some embodiments, R4′ is substituted alkyl(C≤6). In some embodiments, R4′ is haloalkyl(C≤6). In some embodiments, R4′ is trifluoromethyl.
In some embodiments, R5 is substituted alkyl(C≤12). In some embodiments, R5 is substituted alkyl(C≤6). In some embodiments, R5 is haloalkyl(C≤6). R5 is trifluoromethyl.
In some embodiments, R5′ is substituted alkyl(C≤12). In some embodiments, R5′ is substituted alkyl(C≤6). In some embodiments, R5′ is haloalkyl(C≤6). In some embodiments, R5′ is trifluoromethyl.
In some embodiments, R6 is substituted alkyl(C≤12). In some embodiments, R6 is substituted alkyl(C≤6). In some embodiments, R6 is substituted alkyl(C≤6). In some embodiments, R6 is trifluoromethyl.
In some embodiments, R6′ is substituted alkyl(C≤12). In some embodiments, R6′ is substituted alkyl(C≤6). In some embodiments, R6′ is substituted alkyl(C≤6). In some embodiments, R6′ is trifluoromethyl.
In some embodiments, R7 is substituted alkyl(C≤12). In some embodiments, R7 is substituted alkyl(C≤6). In some embodiments, R7 is substituted alkyl(C≤6). In some embodiments, R7 is trifluoromethyl. In some embodiments, R7′ is substituted alkyl(C≤12).
In some embodiments, R7′ is substituted alkyl(C≤6). In some embodiments, R7′ is substituted alkyl(C≤6). In some embodiments, R7′ is trifluoromethyl.
In some embodiments, R8 is substituted alkyl(C≤12). In some embodiments, R8 is substituted alkyl(C≤6). In some embodiments, R8 is substituted alkyl(C≤6). In some embodiments, R8 is trifluoromethyl.
In some embodiments, R8′ is substituted alkyl(C≤12). In some embodiments, R8′ is substituted alkyl(C≤6). In some embodiments, R8′ is substituted alkyl(C≤6). In some embodiments, R8′ is trifluoromethyl.
In some embodiments, R9 is substituted alkyl(C≤12). In some embodiments, R9 is substituted alkyl(C≤6). In some embodiments, R9 is substituted alkyl(C≤6). In some embodiments, R9 is trifluoromethyl.
In some embodiments, R9′ is substituted alkyl(C≤12). In some embodiments, R9′ is substituted alkyl(C≤6). In some embodiments, R9′ is substituted alkyl(C≤6). In some embodiments, R9′ is trifluoromethyl.
In some embodiments, the composition is further described as:
In another aspect, the present disclosure provides a compound of the formula:
wherein:
In some embodiments, the compound further defined as:
wherein:
In some embodiments, the compound is further defined as:
wherein:
In some embodiments, R11 is substituted alkyl(C≤12). In some embodiments, R11 is substituted alkyl(C≤6). In some embodiments, R11 is trifluoromethyl.
In some embodiments, R11′ is substituted alkyl(C≤12). In some embodiments, R11′ is substituted alkyl(C≤6). In some embodiments, R11′ is trifluoromethyl.
In some embodiments, R12 is substituted alkyl(C≤12). In some embodiments, R12 is substituted alkyl(C≤6). In some embodiments, R12 is trifluoromethyl.
In some embodiments, R12′ is substituted alkyl(C≤12). In some embodiments, R12′ is substituted alkyl(C≤6). In some embodiments, R12′ is trifluoromethyl.
In some embodiments, the compound is further defined as:
In some embodiments, R13 is ethylene. In some embodiments, R13 is propylene.
In some embodiments, the compound is further defined as an organometallic complex.
In yet another aspect, there is provided a separation device comprising a compound of the present aspects and embodiments thereof.
A further aspect provides a method of separating an alkene(C≤12) or substituted alkene(C≤12) from an alkane(C≤12) or substituted alkane(C≤12) comprising contacting a mixture comprising an alkene(C≤12) or substituted alkene(C≤12) and an alkane(C≤12) or substituted alkane(C≤12) with a compound according to the present aspects and embodiments thereof.
In some embodiments, the mixture is a gas. In some embodiments, the method comprises a step of removing the alkane(C≤12) or substituted alkane(C≤12). In some embodiments, the alkane(C≤12) or substituted alkane(C≤12) is removed by refluxing the compound in an organic solvent.
In some embodiments, the organic solvent is an alkane(C≤8). In some embodiments, the organic solvent is hexanes.
In some embodiments, the alkane(C≤12) or substituted alkane(C≤12) is removed under reduced pressure. In some embodiments, the reduced pressure is less than 1 bar.
In some embodiments, the temperature is from about 25° C. to about 75° C. In some embodiments, the temperature is from about 30° C. to about 50° C. In some embodiments, the mixture is contacted with the composition at a temperature from about 0° C. to about 75° C. In some embodiments, the temperature is from about 20°° C. to about 50°° C. In some embodiments, the temperature is from about 20° C. to about 30° C.
In some embodiments, the alkane(C≤12) or substituted alkane(C≤12) is ethane. In some embodiments, the alkene(C≤12) or substituted alkene(C≤12) is ethylene.
In some embodiments, the alkane(C≤12) or substituted alkane(C≤12) is propane. In some embodiments, the alkene(C≤12) or substituted alkene(C≤12) is propylene.
In another aspect, there is provided a method of separating propylene from propane comprising contacting a mixture comprising propylene and propane with a compound of the present aspects and embodiments thereof.
In yet another aspect, there is provided a method of separating ethylene from ethane comprising contacting a mixture comprising ethylene and ethane with a compound of the present aspects and embodiments thereof.
Other objects, features and advantages of the present disclosure will become apparent from the following detailed description. It should be understood, however, that the detailed description and the specific examples, while indicating specific embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
The following drawings form part of the present specification and are included to further demonstrate certain aspects of the present disclosure. The invention may be better understood by reference to one of these drawings in combination with the detailed description of specific embodiments presented herein.
Purification of C2H4 from a C2H4/C2H6 mixture is a difficult separation process, which is achieved mainly through energy-intensive, cryogenic distillation in industry. Sustainable, non-distillation methods are desired as alternatives. Provided herein fluorinated bis(pyrazolyl)borate ligand supported copper(I) complex {[(CF3)2Bp]Cu}3 has features desirable in an olefin-paraffin separation material. It binds ethylene exclusively over ethane generating [(CF3)2Bp]Cu(C2H4). This molecular sorbent exhibits extremely high and record IAST C2H4/C2H6 gas separation selectivity, affording high purity (>99.5%) ethylene that can be readily desorbed from separation columns. In-situ PXRD provides a “live” picture of the reversible conversion between [(CF3)2Bp]Cu(C2H4) and the ethylene free sorbent in the solid- state driven by the presence or removal of C2H4. Crystal structures of trinuclear {[(CF3)2Bp]Cu}3 and mononuclear [(CF3)2Bp]Cu(C2H4) are also provided herein.
In certain aspects, the present disclosure provides a molecular sorbent based on copper and a popular ligand class that provides high-purity ethylene from ethylene-ethane mixtures and high-purity propylene from propylene-propane mixtures. Although [(CF3)2Tp]Cu(C2H4) (2) is too inert for this purpose, the inventors discovered that the fluorinated bis(pyrazolyl)borate [(CF3)2Bp]Cu(C2H4) (3) (based on a ligand that is missing a pyrazolyl arm from 2,
A “molecular sorbent” is a molecular species used to recover liquids or gases through the mechanism of absorption, or adsorption, or both.
A “metal organic complex” or “organometallic complex” is used herein to refer to a compound with least one metal-to-carbon bond in which the carbon is part of an organic group.
In addition, atoms making up the compounds of the present invention are intended to include all isotopic forms of such atoms. Isotopes, as used herein, include those atoms having the same atomic number but different mass numbers. By way of general example and without limitation, isotopes of hydrogen include tritium and deuterium, and isotopes of carbon include 13C and 14C. Additionally, it is contemplated that one or more of the metal atoms may be replaced by another isotope of that metal. In some embodiments, the calcium atoms can be 40Ca, 42Ca, 43Ca, 44Ca, 46Ca, or 48Ca. Similarly, it is contemplated that one or more carbon atom(s) of a compound of the present invention may be replaced by a silicon atom(s). Furthermore, it is contemplated that one or more oxygen atom(s) of a compound of the present invention may be replaced by a sulfur or selenium atom(s).
Any undefined valency on a carbon atom of a structure shown in this application implicitly represents a hydrogen atom bonded to the atom.
The use of the word “a” or “an,” when used in conjunction with the term “comprising” in the claims and/or the specification may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.”
Throughout this application, the term “about” is used to indicate that a value includes the inherent variation of error for the device, the method being employed to determine the value, or the variation that exists among the study subjects.
The terms “comprise,” “have” and “include” are open-ended linking verbs. Any forms or tenses of one or more of these verbs, such as “comprises,” “comprising,” “has,” “having,” “includes” and “including,” are also open-ended. For example, any method that “comprises,” “has” or “includes” one or more steps is not limited to possessing only those one or more steps and also covers other unlisted steps.
The term “effective,” as that term is used in the specification and/or claims, means adequate to accomplish a desired, expected, or intended result.
The term “hydrate” when used as a modifier to a compound means that the compound has less than one (e.g., hemihydrate), one (e.g., monohydrate), or more than one (e.g., dihydrate) water molecules associated with each compound molecule, such as in solid forms of the compound.
The term “saturated” when referring to an atom means that the atom is connected to other atoms only by means of single bonds.
When used in the context of a chemical group: “hydrogen” means —H; “hydroxy” means —OH; “oxo” means ═O; “carbonyl” means —C(═O)—; “carboxy” means —C(═O)OH (also written as —COOH or —CO2H); “halo” means independently —F, —Cl, —Br or —I; “amino” means —NH2; “hydroxyamino” means —NHOH; “nitro” means —NO2; imino means ═NH; “cyano” means —CN; “isocyanyl” means —N═C═O; “azido” means 'N3; in a monovalent context “phosphate” means —OP(O)(OH)2 or a deprotonated form thereof, in a divalent context “phosphate” means —OP(O)(OH)O— or a deprotonated form thereof; “mercapto” means —SH; and “thio” means ═S; “thiocarbonyl” means —C(═S)—; “sulfonyl” means —S(O)2—; and “sulfinyl” means —S(O)—.
In the context of chemical formulas, the symbol “—” means a single bond, “═” means a double bond, and “≡” means triple bond. The symbol “- - - -” represents an optional bond, which if present is either single or double. The symbol “” represents a single bond or a double bond. Thus, the formula
covers, for example,
And it is understood that no one such ring atom forms part of more than one double bond. Furthermore, it is noted that the covalent bond symbol “—”, when connecting one or two stereogenic atoms, does not indicate any preferred stereochemistry. Instead, it covers all stereoisomers as well as mixtures thereof. The symbol “”, when drawn perpendicularly across a bond (e.g.,
for methyl) indicates a point of attachment of the group. It is noted that the point of attachment is typically only identified in this manner for larger groups in order to assist the reader in unambiguously identifying a point of attachment. The symbol “” means a single bond where the group attached to the thick end of the wedge is “out of the page.” The symbol “
” means a single bond where the group attached to the thick end of the wedge is “into the page”. The symbol “
” means a single bond where the geometry around a double bond (e.g., either E or Z) is undefined. Both options, as well as combinations thereof are therefore intended. Any undefined valency on an atom of a structure shown in this application implicitly represents a hydrogen atom bonded to that atom. A bold dot on a carbon atom indicates that the hydrogen attached to that carbon is oriented out of the plane of the paper.
The bond orders described above are not limiting when one of the atoms connected by the bond is a metal atom (M). In such cases, it is understood that the actual bonding may comprise significant multiple bonding and/or ionic character. Therefore, unless indicated otherwise, the formulas M—C, M═C, M - - - - C, and MC, each refers to a bond of any and type and order between a metal atom and a carbon atom.
For the chemical groups and compound classes, the number of carbon atoms in the group or class is as indicated as follows: “Cn” or “C=n” defines the exact number (n) of carbon atoms in the group/class. “C≤n” defines the maximum number (n) of carbon atoms that can be in the group/class, with the minimum number as small as possible for the group/class in question. For example, it is understood that the minimum number of carbon atoms in the groups “alkyl(C≤8)”, “alkanediyl(C≤8)”, “heteroaryl(C≤8)”, and “acyl(C≤8)” is one, the minimum number of carbon atoms in the groups “alkenyl(C≤8)”, “alkynyl(C≤8)”, and “heterocycloalkyl(C≤8)” is two, the minimum number of carbon atoms in the group “cycloalkyl(C≤8)” is three, and the minimum number of carbon atoms in the groups “aryl(C≤8)” and “arenediyl(C≤8)” is six. “Cn-n” defines both the minimum (n) and maximum number (n′) of carbon atoms in the group. Thus, “alkyl(C2-10)” designates those alkyl groups having from 2 to 10 carbon atoms. These carbon number indicators may precede or follow the chemical groups or class it modifies and it may or may not be enclosed in parenthesis, without signifying any change in meaning. Thus, the terms “C1-4-alkyl”, “C1-4-alkyl”, “alkyl(C1-4)”, and “alkyl(C≤4)” are all synonymous. Except as noted below, every carbon atom is counted to determine whether the group or compound falls with the specified number of carbon atoms. For example, the group dihexylamino is an example of a dialkylamino(C≤12) group; however, it is not an example of a dialkylamino(C6) group. Likewise, phenylethyl is an example of an aralkyl(C≤8) group. When any of the chemical groups or compound classes defined herein is modified by the term “substituted”, any carbon atom in the moiety replacing the hydrogen atom is not counted. Thus methoxyhexyl, which has a total of seven carbon atoms, is an example of a substituted alkyl(C1-6). Unless specified otherwise, any chemical group or compound class listed in a claim set without a carbon atom limit has a carbon atom limit of less than or equal to twelve.
The term “saturated” when used to modify a compound or chemical group means the compound or chemical group has no carbon-carbon double and no carbon-carbon triple bonds, except as noted below. When the term is used to modify an atom, it means that the atom is not part of any double or triple bond. In the case of substituted versions of saturated groups, one or more carbon oxygen double bond or a carbon nitrogen double bond may be present. And when such a bond is present, then carbon-carbon double bonds that may occur as part of keto- enol tautomerism or imine/enamine tautomerism are not precluded. When the term “saturated” is used to modify a solution of a substance, it means that no more of that substance can dissolve in that solution.
The term “aliphatic” signifies that the compound or chemical group so modified is an acyclic or cyclic, but non-aromatic compound or group. In aliphatic compounds/groups, the carbon atoms can be joined together in straight chains, branched chains, or non-aromatic rings (alicyclic). Aliphatic compounds/groups can be saturated, that is joined by single carbon- carbon bonds (alkanes/alkyl), or unsaturated, with one or more carbon-carbon double bonds (alkenes/alkenyl) or with one or more carbon-carbon triple bonds (alkynes/alkynyl).
The term “aromatic” signifies that the compound or chemical group so modified has a planar unsaturated ring of atoms with 4n+2 electrons in a fully conjugated cyclic π system. An aromatic compound or chemical group may be depicted as a single resonance structure; however, depiction of one resonance structure is taken to also refer to any other resonance structure. For example:
Aromatic compounds may also be depicted using a circle to represent the delocalized nature of the electrons in the fully conjugated cyclic π system, two non-limiting examples of which are shown below:
The term “alkyl” refers to a monovalent saturated aliphatic group with a carbon atom as the point of attachment, a linear or branched acyclic structure, and no atoms other than carbon and hydrogen. The groups —CH3 (Me), —CH2CH3 (Et), —CH2CH2CH3 (n-Pr or propyl), —CH(CH3)2 (i-Pr, iPr or isopropyl), —CH2CH2CH2CH3 (n-Bu), —CH(CH3)CH2CH3 (sec-butyl), —CH2CH(CH3)2 (isobutyl), —C(CH3)3 (tert-butyl, t-butyl, t-Bu or tBu), and —CH2C(CH3)3 (neo-pentyl) are non-limiting examples of alkyl groups. The term “alkanediyl” refers to a divalent saturated aliphatic group, with one or two saturated carbon atom(s) as the point(s) of attachment, a linear or branched acyclic structure, no carbon-carbon double or triple bonds, and no atoms other than carbon and hydrogen. The groups —CH2— (methylene), —CH2CH2—, —CH2C(CH3)2CH2—, and —CH2CH2CH2— are non-limiting examples of alkanediyl groups. The term “alkylidene” refers to the divalent group ═CRR′ in which R and R′ are independently hydrogen or alkyl. Non-limiting examples of alkylidene groups include: ═CH2, ═CH(CH2CH3), and ═C(CH3)2. An “alkane” refers to the class of compounds having the formula H—R, wherein R is alkyl as this term is defined above.
The term “cycloalkyl” refers to a monovalent saturated aliphatic group with a carbon atom as the point of attachment, said carbon atom forming part of one or more non-aromatic ring structures, no carbon-carbon double or triple bonds, and no atoms other than carbon and hydrogen. Non-limiting examples include: —CH(CH2)2 (cyclopropyl), cyclobutyl, cyclopentyl, or cyclohexyl (Cy). As used herein, the term does not preclude the presence of one or more alkyl groups (carbon number limitation permitting) attached to a carbon atom of the non-aromatic ring structure. The term “cycloalkanediyl” refers to a divalent saturated aliphatic group with two carbon atoms as points of attachment, no carbon-carbon double or triple bonds, and no atoms other than carbon and hydrogen. The group
is a non-limiting example of cycloalkanediyl group. A “cycloalkane” refers to the class of compounds having the formula H—R, wherein R is cycloalkyl as this term is defined above.
The term “alkenyl” refers to a monovalent unsaturated aliphatic group with a carbon atom as the point of attachment, a linear or branched, acyclic structure, at least one nonaromatic carbon-carbon double bond, no carbon-carbon triple bonds, and no atoms other than carbon and hydrogen. Non-limiting examples include: —CH═CH2 (vinyl), —CH═CHCH3, —CH═CHCH2CH3, —CH2CH═CH2 (allyl), —CH2CH═CHCH3, and —CH═CHCH═CH2. The term “alkenediyl” refers to a divalent unsaturated aliphatic group, with two carbon atoms as points of attachment, a linear or branched acyclic structure, at least one nonaromatic carbon-carbon double bond, no carbon-carbon triple bonds, and no atoms other than carbon and hydrogen. The groups —CH—CH—, —CH═C(CH3)CH2—, —CH═CHCH2—, and —CH2CH═CHCH2— are non-limiting examples of alkenediyl groups. It is noted that while the alkenediyl group is aliphatic, once connected at both ends, this group is not precluded from forming part of an aromatic structure. The terms “alkene” and “olefin” are synonymous and refer to the class of compounds having the formula H—R, wherein R is alkenyl as this term is defined above. Similarly, the terms “terminal alkene” and “α-olefin” are synonymous and refer to an alkene having just one carbon-carbon double bond, wherein that bond is part of a vinyl group at an end of the molecule.
The term “alkynyl” refers to a monovalent unsaturated aliphatic group with a carbon atom as the point of attachment, a linear or branched acyclic structure, at least one carbon- carbon triple bond, and no atoms other than carbon and hydrogen. As used herein, the term alkynyl does not preclude the presence of one or more non-aromatic carbon-carbon double bonds. The groups —C≡CH, —C≡CCH3, and —CH2C≡CCH3 are non-limiting examples of alkynyl groups. An “alkyne” refers to the class of compounds having the formula H—R, wherein R is alkynyl.
The term “aryl” refers to a monovalent unsaturated aromatic group with an aromatic carbon atom as the point of attachment, said carbon atom forming part of a one or more aromatic ring structures, each with six ring atoms that are all carbon, and wherein the group consists of no atoms other than carbon and hydrogen. If more than one ring is present, the rings may be fused or unfused. Unfused rings are connected with a covalent bond. As used herein, the term aryl does not preclude the presence of one or more alkyl groups (carbon number limitation permitting) attached to the first aromatic ring or any additional aromatic ring present. Non-limiting examples of aryl groups include phenyl (Ph), methylphenyl, (dimethyl)phenyl, —C6H4CH2CH3 (ethylphenyl), naphthyl, and a monovalent group derived from biphenyl (e.g., 4-phenylphenyl). The term “arenediyl” refers to a divalent aromatic group with two aromatic carbon atoms as points of attachment, said carbon atoms forming part of one or more six-membered aromatic ring structures, each with six ring atoms that are all carbon, and wherein the divalent group consists of no atoms other than carbon and hydrogen. As used herein, the term arenediyl does not preclude the presence of one or more alkyl groups (carbon number limitation permitting) attached to the first aromatic ring or any additional aromatic ring present. If more than one ring is present, the rings may be fused or unfused. Unfused rings are connected with a covalent bond. Non-limiting examples of arenediyl groups include:
An “arene” refers to the class of compounds having the formula H—R, wherein R is aryl as that term is defined above. Benzene and toluene are non-limiting examples of arenes.
The term “acyl” refers to the group —C(O)R, in which R is a hydrogen, alkyl, cycloalkyl, or aryl as those terms are defined above. The groups, —CHO, —C(O)CH3 (acetyl, Ac), —C(O)CH2CH3, —C(O)CH(CH3)2, —C(O)CH(CH2)2, —C(O)C6H5, and —C(O)C6H4CH3 are non-limiting examples of acyl groups. A “thioacyl” is defined in an analogous manner, except that the oxygen atom of the group —C(O)R has been replaced with a sulfur atom, C(S)R. The term “aldehyde” corresponds to an alkyl group, as defined above, attached to a —CHO group.
The term “alkoxy” refers to the group —OR, in which R is an alkyl, as that term is defined above. Non-limiting examples include: —OCH3 (methoxy), —OCH2CH3 (ethoxy), —OCH2CH2CH3, —OCH(CH3)2 (isopropoxy), or —OC(CH3); (tert-butoxy). The terms “cycloalkoxy”, “alkenyloxy”, “alkynyloxy”, “aryloxy”, “aralkoxy”, “heteroaryloxy”, “heterocycloalkoxy”, and “acyloxy”, when used without the “substituted” modifier, refers to groups, defined as —OR, in which R is cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heteroaryl, heterocycloalkyl, and acyl, respectively. The term “alkylthio” and “acylthio” refers to the group —SR, in which R is an alkyl and acyl, respectively. The term “alcohol” corresponds to an alkane, as defined above, wherein at least one of the hydrogen atoms has been replaced with a hydroxy group. The term “ether” corresponds to an alkane, as defined above, wherein at least one of the hydrogen atoms has been replaced with an alkoxy group.
When a chemical group is used with the “substituted” modifier, one or more hydrogen atom has been replaced, independently at each instance, by —OH, —F, —Cl, —Br, —I, —NH2, —NO2, —CO2H, —CO2CH3, —CO2CH2CH3, —CN, —SH, —OCH3, —OCH2CH3, —C(O)CH3, —NHCH3, —NHCH2CH3, —N(CH3)2, —C(O)NH2, —C(O)NHCH3, —C(O)N(CH3)2, —OC(O)CH3, —NHC(O)CH3, —S(O)2OH, or —S(O)2NH2. For example, the following groups are non-limiting examples of substituted alkyl groups: CH2OH, —CH2Cl, —CF3, —CH2CN, —CH2C(O)OH, —CH2C(O)OCH3—CH2C(O)NH2, —CH2C(O)CH3, —CH2OCH3, —CH2OC(O)CH3, —CH2NH2, —CH2N(CH3)2, and —CH2CH2Cl. The term “haloalkyl” is a subset of substituted alkyl, in which the hydrogen atom replacement is limited to halo (i.e. —F, —Cl, —Br, or —I) such that no other atoms aside from carbon, hydrogen and halogen are present. The group, —CH2Cl is a non-limiting example of a haloalkyl. The term “fluoroalkyl” is a subset of substituted alkyl, in which the hydrogen atom replacement is limited to fluoro such that no other atoms aside from carbon, hydrogen and fluorine are present. The groups —CH2F, —CF3, and —CH2CF3 are non-limiting examples of fluoroalkyl groups. Non-limiting examples of substituted aralkyls are: (3-chlorophenyl)-methyl, and 2-chloro-2-phenyl-eth-1-yl. The groups, —C(O)CH2CF3, —CO2H (carboxyl), —CO2CH3 (methylcarboxyl), —CO2CH2CH3, —C(O)NH2 (carbamoyl), and —CON(CH3)2, are non-limiting examples of substituted acyl groups. The groups —NHC(O)OCH3 and —NHC(O)NHCH3 are non-limiting examples of substituted amido groups. “Metal-organic frameworks” (MOFs) are framework materials, typically three-dimensional, self-assembled by the coordination of metal ions with organic linkers exhibiting porosity, typically established by gas adsorption. The MOFs discussed and disclosed herein are at times simply identified by their repeat unit as defined below without brackets or the subscript n. A mixed-metal-organic frameworks (M′MOF) is a subset of MOFs having two of more types of metal ions.
The term “unit cell” is basic and least volume consuming repeating structure of a solid. The unit cell is described by its angles between the edges (α, β, γ) and the length of these edges (a, b, c). As a result, the unit cell is the simplest way to describe a single crystal X-ray diffraction pattern.
A “repeat unit” is the simplest structural entity of certain materials, for example, frameworks and/or polymers, whether organic, inorganic or metal-organic. In the case of a polymer chain, repeat units are linked together successively along the chain, like the beads of a necklace. For example, in polyethylene, —[—CH2CH2—]n—, the repeat unit is —CH2CH2—. The subscript “n” denotes the degree of polymerization, that is, the number of repeat units linked together. When the value for “n” is left undefined, it simply designates repetition of the formula within the brackets as well as the polymeric and/or framework nature of the material. The concept of a repeat unit applies equally to where the connectivity between the repeat units extends into three dimensions, such as in metal organic frameworks, cross-linked polymers, thermosetting polymers, etc. Note that for MOFs the repeat unit may also be shown without the subscript n.
“Pores” or “micropores” in the context of metal-organic frameworks are defined as open space within the MOFs; pores become available, when the MOF is activated for the storage of gas molecules. Activation can be achieved by heating, e.g., to remove solvent molecules.
“Multimodal size distribution” is defined as pore size distribution in three dimensions.
“Multidentate organic linker” is defined as ligand having several binding sites for the coordination to one or more metal ions.
The above definitions supersede any conflicting definition in any of the reference that is incorporated herein by reference. The fact that certain terms are defined, however, should not be considered as indicative that any term that is undefined is indefinite. Rather, all terms used are believed to describe the invention in terms such that one of ordinary skill can appreciate the scope and practice the present invention.
The following examples are included to demonstrate preferred embodiments of the disclosure. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor to function well in the practice of the disclosure, and thus can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the disclosure.
It was discovered that the fluorinated bis(pyrazolyl)borate [(CF3)2Bp]Cu(C2H4) (3) (based on a ligand that is missing a pyrazolyl arm from 2,
Treatment of [(CF3)2Bp]Cu(NCMe) (Dias et al., 2005) with ethylene in dichloromethane at room temperature led to the displacement of acetonitrile ligand from copper and the formation of copper(I) ethylene complex [(CF3)2Bp]Cu(C2H4) (3) in 92% isolated yield. It is a colorless, thermally stable solid that can be handled in air for hours without decomposition. The ethylene protons of 3 in the 1H NMR spectrum appear at δ 4.69 ppm. This points to an intermediate level of olefinic proton shielding relative to those of 1 (δ 4.41 ppm) and 2 (δ 4.96 ppm). The presence of additional ethylene leads to separate broad signals of free and coordinated ethylene indicating associative olefin exchange. In contrast, coordinatively saturated 2 does not exchange with free ethylene at room temperature. The 13C{1H} NMR spectrum of [(CF3)2Bp]Cu(C2H4) (3) in CDCl3 shows a peak at δ 86.6 ppm corresponding to the carbons of the copper bound ethylene moiety, which is an upfield shift (of 36.5 ppm) compared to the corresponding resonance of the free C2H4, δ 123.1 ppm. The
More importantly, it is possible to remove the coordinated C2H4 from solid 3 using reduced pressure with mild heat (˜40° C.) or by refluxing a solution of 3 in hexanes. The resulting ethylene-free product {[(CF3)2Bp]Cu}3 (4) converts readily back to 3 upon treatment with C2H4 (1 atm) in solution (
Remarkably, the ethylene-driven transformation of copper(I) sorbent to mononuclear [(CF3)2Bp]Cu(C2H4) also occurs in dense crystalline materials in the solid-state. To confirm this, in-situ PXRD measurements were performed at 17-BM beamline at the Advanced Photon Source, Argonne National Laboratory. It is possible to remove ethylene from [(CF3)2Bp]Cu(C2H4) in a flow of helium under gentle heating, and generate the ethylene free copper sorbent (
To evaluate the adsorptive separation of C2H4 and C2H6 on {[(CF3)2Bp]Cu}3, single-component adsorption isotherms of the two gases were collected at 298 K. It was shown that the adsorption isotherm for C2H4 on {[(CF3)2Bp]Cu}; exhibited a steep slope at relatively low pressure, indicating a strong affinity of {[(CF3)2Bp]Cu}3 towards C2H4 molecules (
In a typical ethylene production process based on the cracking of heavier hydrocarbon fractions followed by dehydrogenation reactions, resulting in conversion yield of only around 50-60% (Faiz et al., 2012). Thus, the separation of C2H4 from the C2H4/C2H6 mixture is needed before further utilization. To evaluate the performance of {[(CF3)2Bp]Cu}3 in an adsorptive dynamic separation process, breakthrough experiments were performed, in which an equimolar C2H4/C2H6 mixture flowed over a packed column of the activated {[(CF3)2Bp]Cu}3 solid with a rate of 2 mL min−1 at 298 K (
Further, C3H6 capture capability was assessed by breakthrough experiments with a C3H6/C3H8 (50:50, V:V) gas mixture through a packed column with the activated sample under ambient conditions with a flow rate of 2.0 mL/min (
In summary, an effective, molecular sorbent {[(CF3)2Bp]Cu}3 has been uncovered for C2H4/C2H6 and C3H6/C3H8 separation. The ethylene uptake was investigated by {[(CF3)2Bp]Cu}3 and removal from [(CF3)2Bp]Cu(C2H4) in solution, as well as in the solid-state. Similarly, the propylene uptake was investigated by {[(CF3)2Bp]Cu}3 and removal from [(CF3)2Bp]Cu(C3H6) in solution. Complete characterization of these interesting molecular species including their crystal structures has been achieved. Furthermore, in-situ PXRD provides a complete “live” picture of the solid-state process that also retains the precursor and product crystallinity and undergoes fast and complete and reversible conversion between the copper based sorbent and [(CF3)2Bp]Cu(C2H4) driven by the presence or removal of C2H4. The accessible Cu(I) sites within this molecular compound have enabled it to exclusively bind ethylene over ethane, so this molecular sorbent exhibits extremely high and record IAST C2H4/C2H6 gas separation selectivity. The superior ethylene separation and purification performance of this molecular sorbent have been further confirmed by the breakthrough experiments in which ethylene of a purity level of over 99.5% can be readily desorbed from the separation columns. Similarly, it was shown that neat separation of C3H6 from C3H8 by the activated sample could be successfully achieved.
[(CF3)2Bp]Cu(C2H4) (3): (
{[(CF3)2Bp]Cu}3 (4): (
[(CF3)2Bp]Cu(C3H6): (
All manipulations were carried out under an atmosphere of purified nitrogen using standard Schlenk techniques or in a MBraun glovebox equipped with a −25° C. refrigerator. Solvents were purchased from commercial sources, purified before use. NMR spectra were recorded at 25° C. on a JEOL Eclipse 500 spectrometer (1H, 500.16 MHz 13C, 125.78 MHz, and 19F, 470.62 MHz) unless otherwise noted. 1H and 13C NMR spectra are referenced to the solvent peak (1H; CDCl3 δ 7.26, CD2Cl2 δ 5.32, (CD3)2SO δ 2.5, 13C; CDCl3 δ 77.16, (CD3)2SO δ 39.52). 1H NMR coupling constants (J) are reported in Hertz (Hz) and multiplicities are indicated as follows: s (singlet), d (doublet), t (triplet), m (multiplet). 19F NMR values were referenced to external CFCl3. Melting points were obtained on a Mel-Temp II apparatus and were not corrected. Elemental analyses were performed using a Perkin-Elmer Model 2400 CHN analyzer. IR spectra were collected at room temperature on a Shimadzu IR Prestige-21 FTIR containing an ATR attachment using pure liquid or solid materials, with instrument resolution at 2 cm−1. Raman data were collected on a Horiba Jobin Yvon LabRAM Aramin Raman spectrometer with a HeNe laser source of 633 nm, by placing pure solid materials on a glass slide. All other reactants and reagents were purchased from commercial sources. Heating was accomplished by either a heating mantle or a silicone oil bath. [(CF3)2Bp]Cu(NCMe)1 was prepared via reported methods.
1H NMR
13C{1H} NMR
X-ray Data Collection and Structure Determinations. A suitable crystal covered with a layer of hydrocarbon/Paratone-N oil was selected and mounted on a Cryo-loop, and immediately placed in the low-temperature nitrogen stream. The X-ray intensity data were measured at 100(2) K on a Bruker D8 Quest with a Photon 100 CMOS detector equipped with an Oxford Cryosystems 700 series cooler, a graphite monochromator, and a Mo Kα fine-focus sealed tube (λ=0.71073 Å). Intensity data were processed using the Bruker Apex program suite. Absorption corrections were applied by using SADABS (Krause et al., 2015. Initial atomic positions were located by SHELXT (Sheldrick, 2015-a), and the structures of the compounds were refined by the least-squares method using SHELXL (Sheldrick, 2015-b) within Olex2 GUI (Dolomanov et al., 2009). All the non-hydrogen atoms were refined anisotropically. The hydrogen atoms of ethylene and BH2 moieties of [(CF3)2Bp]Cu(C2H4) and {[(CF3)2Bp]Cu}3 were located in difference Fourier maps, included and refined freely with isotropic displacement parameters. The remaining hydrogen atoms were included in their calculated positions and refined as riding on the atoms to which they are joined. X-ray structural figures were generated using Olex2 (Dolomanov et al., 2009). CCDC 2088726-2088727 files contain the supplementary crystallographic data. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre (CCDC), 12 Union Road, Cambridge, CB2 1EZ, UK).
The {[(CF3)2Bp]Cu}3 crystallizes with disordered lattice solvent molecules, n-hexane. The presence of a solvent molecule could easily be seen by the residual peaks, consistent with a carbon chain, located in the open channels. Unfortunately, it was disordered over multiple positions, and also lies on a symmetry element, and therefore could not be modeled satisfactorily even with restraints. Consequently, it was removed from the electron density map using Olex2 Solvent Mask command. Based on this solvent mask calculation, and 188 electrons were found in a volume of 800 A3 in 2 voids per unit cell. This is consistent with the presence of 0.5[C6H14] per Asymmetric Unit which accounts for 200 electrons per unit cell.
11 − X, +Y, 1/2 − Z
Single-component gas sorption measurement. The gas sorption isotherms were collected on an automatic volumetric adsorption apparatus (Micromeritics ASAP 2020 surface area analyzer). Before the sorption measurements, the as-synthesized sample was dried under high vacuum for 12 h at 313 K, giving the activated {[(CF3)2Bp]Cu}3 (4) for gas sorption analyses.
Fitting of pure-component isotherms. The pure-component isotherm data for C2H4 and C2H6 in {[(CF3)2Bp]Cu}3 (4) was fitted with the single-site Langmuir-Freundlich model.
where p (unit: kPa) is the pressure of the bulk gas at equilibrium with the adsorbed phase, N (unit: mmol g−1) is the adsorbed amount per mass of adsorbent, Nmax (unit: mmol g−1) is the saturation capacities, b (unit: 1/kPa) is the affinity coefficient and n represents the deviation from an ideal homogeneous surface. The fitted parameter values are presented in Table 8.
IAST calculations of adsorption selectivities. The adsorption selectivity for C2H4/C2H6 separation is defined by
q1 and q2 are the molar loadings in the adsorbed phase in equilibrium with the bulk gas phase with partial pressures p1 and p2.
Breakthrough separation experiments. The breakthrough experiments were carried out in dynamic gas breakthrough set-up. A stainless-steel column with inner dimensions of 4×81 mm was used for sample packing. Microcrystalline sample (1.1597 g) was then packed into the column. The column was placed in a temperature-controlled environment (maintained at 298 K). The mixed gas flow and pressure were controlled by using a pressure control valve and a mass flow controller (
In situ synchrotron powder diffraction data collection (XRD). In situ powder diffraction data of copper complexes in ethylene and He atmosphere were collected using the monochromatic X-rays available at the 17-BM. A beam (300 μm diameter beam size) with 0.45238 Å wavelength was used at the Advanced Photon Source, Argonne National Laboratory in combination with a VAREX 4343 amorphous-Si flat panel detector. A sample of analytically pure [(CF3)2Bp]Cu(C2H4) was loaded into 1.0 mm quartz capillaries with glass wool on either side. The capillary with sample was then loaded into the gas flow-cell (Chupas et al., 2008), to perform in situ PXRD experiments. At one end the gas cell was connected to a two-way valve which allowed changing between a 1 atm helium flow and a high-pressure syringe pump (Teledyne ISCO 500D) which was filled with ethene gas.
Data Processing. The raw images were processed within GSAS-II (Toby et al., 2013), refining the sample-to-detector distance and tilt of the detector relative to the beam based on data obtained for a LaB6 standard (Hammersley et al., 1996) Collected and integrated in situ powder diffraction data sets were trimmed, normalized and plotted using 2DFLT software (Yakovenko et al., 2014).
Ethylene desorption experiment. The ethylene desorption experiment started with the pure [(CF3)2Bp]Cu(C2H4) sample in the capillary. It was heated under helium flow as ethylene desorption was allow to proceed, while monitoring composition of the system by PXRD. At around 320K, significant ethylene loss (peak position and intensity change) was started and completed at around 343K. This observation is consistent with data from NMR experiments and the synthesis of ethylene free {[(CF3)2Bp]Cu}3 noted in the manuscript via separate routes.
Ethylene loading experiment. After several PXRD scans of in-situ generated sorbent, the gas flow cell was connected to the syringe pump and helium gas in the capillary was exchanged with an ethylene flow of 1 bar (100 kPa). There was peak position and intensity change immediately after application of ethylene pressure to the ethylene free sorbent, indicating formation of new crystallographic phase which was same as the [(CF3)2Bp]Cu(C2H4).
All of the compounds, material, compositions, and methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the disclosure may have focused on several embodiments or may have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations and modifications may be applied to the compounds, compositions, and methods without departing from the spirit, scope, and concept of the invention. All variations and modifications apparent to those skilled in the art are deemed to be within the spirit, scope, and concept of the invention as defined by the appended claims.
The following references, to the extent that they provide exemplary procedural or other details supplementary to those set forth herein, are specifically incorporated herein by reference.
Nat. Mater., 17 (12), 1128-1133, 2018.
This application claims the benefit of priority to U.S. Provisional Application No. 63/218,569, filed on Jul. 6, 2021, the entire content of which are hereby incorporated by reference. This invention was made with government support under Grant No. CHE-1954456 awarded by the National Science Foundation (NSF). The government has certain rights in the invention.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2022/073461 | 7/6/2022 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 63218569 | Jul 2021 | US |
