Metal-organic frameworks for aromatic hydrocarbon separations
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IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C07F-015/00
C07C-007/12
C07F-015/06
B01J-020/22
B01D-053/02
C10G-025/00
B01D-015/08
B01D-015/38
B01D-053/04
B01D-053/047
출원번호
US-0957494
(2015-12-02)
등록번호
US-10118877
(2018-11-06)
발명자
/ 주소
Long, Jeffrey R.
Bloch, Eric D.
Kapelewski, Matthew
Gonzalez, Miguel Carlos I.
출원인 / 주소
The Regents of the University of California
대리인 / 주소
Gavrilovich, Dodd & Lindsey LLP
인용정보
피인용 횟수 :
0인용 특허 :
35
초록
The disclosure provides for metal organic frameworks (MOFs) that are selective adsorbents for aromatic hydrocarbons, devices comprising the MOFs thereof, and methods using the MOFS thereof for separating and/or storing aromatic hydrocarbons.
대표청구항▼
1. A metal-organic framework (MOF) comprising a repeating core having the general structure M-L-M, wherein M is a metal or metal ion, and L is a linking moiety comprising a structure of Formula III: wherein, R5-R10 are independently selected from H, D, FG, optionally substituted (C1-C12)alkyl, opti
1. A metal-organic framework (MOF) comprising a repeating core having the general structure M-L-M, wherein M is a metal or metal ion, and L is a linking moiety comprising a structure of Formula III: wherein, R5-R10 are independently selected from H, D, FG, optionally substituted (C1-C12)alkyl, optionally substituted hetero-(C1-C12)alkyl, optionally substituted (C1-C12)alkenyl, optionally substituted hetero-(C1-C12)alkenyl, optionally substituted (C1-C12)alkynyl, optionally substituted hetero-(C1-C12)alkynyl, optionally substituted (C1-C12)cycloalkyl, optionally substituted (C1-C12)cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, —C(R11)3, —CH(R11)2, —CH2R11, —C(R12)3, —CH(R12)2, —CH2R12, —OC(R11)3, OCH(R11)2, —OCH2R11, —OC(R12)3, —OCH(R12)2, OCH2R12;R11 is selected from FG, optionally substituted (C1-C12)alkyl, optionally substituted hetero-(C1-C12)alkyl, optionally substituted (C1-C12)alkenyl, optionally substituted hetero-(C1-C12)alkenyl, optionally substituted (C1-C12)alkynyl, optionally substituted hetero-(C1-C12)alkynyl, hemiacetal, hemiketal, acetal, ketal, and orthoester; andR12 is selected from one or more substituted or unsubstituted rings selected from cycloalkyl, aryl and heterocycle;wherein the MOF comprises coordinatively-unsaturated metal cation sites, and wherein the MOF is a selective adsorbent for aromatic hydrocarbons by having multiple unsaturated metal cation sites that can come into contact with an aromatic hydrocarbon to form multiple metal site-hydrocarbon molecule interactions. 2. The MOF of claim 1, wherein the MOF comprises a repeating core having the general structure M-L-M, wherein M is a metal or metal ion, and L is a linking moiety comprising a structure of Formula III: wherein, R5-R10 are independently selected from H, halo, amino, amide, imine, azide, methyl, cyano, nitro, nitroso, hydroxyl, aldehyde, carbonyl, ester, thiol, sulfinyl, sulfonyl, and thiocyanate. 3. The MOF of claim 1, wherein M is selected from L+, Na+, K+, Rb+, Cs+, Be2+, Mg2+, Ca2+, Sr2+, Ba2+, Sc3+, Sc2+, Sc+, Y3+, Y2+, Y+, Ti4+, Ti3+, Ti2+, Zr4+, Zr3+, Zr2+, Hf4+, Hf3+, V5+, V4+, V3+, V2+, Nb5+, Nb4+, Nb3+, Nb2+, Ta5+, Ta4+, Ta3+, Ta2+, Cr6+, Cr5+, Cr4+, Cr3+, Cr2+, Cr+, Cr, Mo6+, Mo5+, Mo4+, Mo3+, Mo2+, Mo+, Mo, W6+, W5+, W4+, W3+, W2+, W+, W, Mn7+, Mn6+, Mn5+, Mn4+, Mn3+, Mn2+, Mn+, Re7+, Re6+, Re5+, Re4+, Re3+, Re2+, Re+, Re, Fe6+, Fe4+, Fe3+, Fe2+, Fe+, Fe, Ru8+, Ru7+, Ru6+, Ru4+, Ru3+, Ru2+, Os8+, Os7+, Os6+, Os5+, Os4+, Os3+, Os2+, Os+, Os, Co5+, Co4+, Co3+, Co2+, Co+, Rh6+, Rh5+, Rh4+, Rh3+, Rh2+, Rh+, Ir6+, Ir5+, Ir4+, Ir3+, Ir2+, Ir+, Ir, Ni3+, Ni2+, Ni+, Ni, Pd6+, Pd4+, Pd2+, Pd+, Pd, Pt6+, Pt5+, Pt4+, Pt3+, Pt2+, Pt+, Cu4+, Cu3+, Cu2+, Cu+, Ag3+, Ag2+, Ag+, Au5+, Au4+, Au3+, Au2+, Au+, Zn2+, Zn+, Zn, Cd2+, Cd+, Hg4+, Hg2+, Hg+, B3+, B2+, B+, Al3+, Al2+, Al+, Ga3+, Ga2+, Ga+, In3+, In2+, In1+, Tl3+, Tl+, Si4+, Si3+, Si2+, Si+, Ge4+, Ge3+, Ge2+, Ge+, Ge, Sn4+, Sn2+, Pb4+, Pb2+, As5+, As3+, As2+, As+, Sb5+, Sb3+, Bi5+, Bi3+, Te6+, Te5+, Te4+, Te2+, La3+, La2+, Ce4+, Ce3+, Ce2+, Pr4+, Pr3+, Pr2+, Nd3+, Nd2+, Sm3+, Sm2+, Eu3+, Eu2+, Gd3+, Gd2+, Gd+, Tb4+, Tb3+, Tb2+, Tb+, Db3+, Db2+, Ho3+, Er3+, Tm4+, Tm3+, Tm2+, Yb3+, Yb2+, Lu3+, La3+, La2+, La+, and combinations thereof, including any complexes which contain the metals or metal ions, as well as any corresponding metal salt counter-anions. 4. The MOF of claim 3, wherein M is selected from Be2+, Mg2+, Ca2+, Sr2+, Ba2+, Sc2+, Y2+, Ti2+, Zr2+, V2+, Nb2+, Ta2+, Cr2+, Mo2+, W2+, Mn2+, Re2+, Fe2+, Ru2+, Os2+, Co2+, Rh2+, Ir2+, Ni2+, Pd2+, Pt2+, Cu2+, Ag2+, Au2+, Zn2+, Cd2+, Hg2+, B2+, Al2+, Ga2+, In2+, Si2+, Ge2+, Sn2+, Pb2+, As2+, Te2+, La2+, Ce2+, Pr2+, Nd2+, Sm2+, Eu2+, Gd2+, Tb2+, Db2+, Tm2+, Yb2+, and La2+, including any complexes which contain the metal ions, as well as any corresponding metal salt counter-anions. 5. The MOF of claim 4, wherein M is Co2+. 6. The MOF of claim 1, wherein the MOF comprises a repeating core of Co2(dobpdc) (dobpdc=4,4′-dioxido-3,3′-biphenyldicarboxylate). 7. The MOF of claim 1, wherein the MOF comprises 1-D hexagonal channels with a high density of 5-coordinate metal centers with a sixth, vacant coordination site pointing into the pores. 8. The MOF of claim 1, wherein the MOF is reacted with a post framework reactant that adds at least one effect to a MOF selected from: modulating the aromatic hydrocarbon storage and/or separation ability of the MOF;modulating the sorption properties of the MOF;modulating the pore size of the MOF; andmodulating the metal-metal separation distance of the MOF. 9. A device comprising a MOF of claim 1 used for separating and/or storing aromatic hydrocarbons. 10. A method of separating and/or storing one or more aromatic hydrocarbons from a mixture comprising aromatic hydrocarbons comprising contacting the mixture with a MOF comprising a repeating core having the general structure M-L-M, wherein M is a metal or metal ion, and L is a linking moiety comprising a structure of Formula I, II and/or Formula III: wherein, R1-R10 are independently selected from H, D, FG, optionally substituted (C1-C12)alkyl, optionally substituted hetero-(C1-C12)alkyl, optionally substituted (C1-C12)alkenyl, optionally substituted hetero-(C1-C12)alkenyl, optionally substituted (C1-C12)alkynyl, optionally substituted hetero-(C1-C12)alkynyl, optionally substituted (C1-C12)cycloalkyl, optionally substituted (C1-C12)cycloalkenyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted mixed ring system, —C(R11)3, —CH(R11)2, —CH2R11, —C(R12)3, —CH(R12)2, —CH2R12, —OC(R11)3, OCH(R11)2, —OCH2R11, —OC(R12)3, —OCH(R12)2, OCH2R12;R11 is selected from FG, optionally substituted (C1-C12)alkyl, optionally substituted hetero-(C1-C12)alkyl, optionally substituted (C1-C12)alkenyl, optionally substituted hetero-(C1-C12)alkenyl, optionally substituted (C1-C12)alkynyl, optionally substituted hetero-(C1-C12)alkynyl, hemiacetal, hemiketal, acetal, ketal, and orthoester; andR12 is selected from one or more substituted or unsubstituted rings selected from cycloalkyl, aryl and heterocycle;wherein the MOF comprises coordinatively-unsaturated metal cation sites, and wherein the MOF is a selective adsorbent for aromatic hydrocarbons by having multiple unsaturated metal cation sites that can come into contact with an aromatic hydrocarbon to form multiple metal site-hydrocarbon molecule interactions. 11. The method of claim 10, wherein the mixture comprises reformates from a catalytic reforming process. 12. The method of claim 10, wherein the mixture comprises aromatic hydrocarbons selected from toluene, ethylbenzene, benzene, para-xylene, meta-xylene, ortho-xylene, durene, mesitylene, biphenyl, naphthalene, anthracene, phenanthrene, and any combination thereof. 13. The method of claim 12, wherein the mixture comprises aromatic hydrocarbons selected from ethylbenzene, para-xylene, meta-xylene, and ortho-xylene. 14. The method of claim 10, wherein the MOF comprises a repeating core having the general structure M-L-M, wherein M is a metal or metal ion, and L is a linking moiety comprising a structure of Formula I, II and/or Formula III: wherein, R1-R10 are independently selected from H, halo, amino, amide, imine, azide, methyl, cyano, nitro, nitroso, hydroxyl, aldehyde, carbonyl, ester, thiol, sulfinyl, sulfonyl, and thiocyanate. 15. The method of claim 10, wherein M is selected from Be2+, Mg2+, Ca2+, Sr2+, Ba2+, Sc2+, Y2+, Ti2+, Zr2+, V2+, Nb2+, Ta2+, Cr2+, Mo2+, W2+, Mn2+, Re2+, Fe2+, Ru2+, Os2+, Co2+, Rh2+, Ir2+, Ni2+, Pd2+, Pt2+, Cu2+, Ag2+, Au2+, Zn2+, Cd2+, Hg2+, B2+, Al2+, Ga2+, In2+, Si2+, Ge2+, Sn2+, Pb2+, As2+, Te2+, La2+, Ce2+, Pr2+, Nd2+, Sm2+, Eu2+, Gd2+, Tb2+, Db2+, Tm2+, Yb2+, and La2+, including any complexes which contain the metal ions, as well as any corresponding metal salt counter-anions. 16. The method of claim 15, wherein M is Co2+. 17. The method of claim 10, wherein the MOF comprises a repeating core of Co2(dobdc), Co2(m-dobdc) or Co2(dobpdc) (dobdc=2,5-dioxido-1,4-benzenedicarboxylate, m-dobdc=4,6-dioxido-1,3-benzenedicarboxylate, dobpdc=4,4′-dioxido-3,3′-biphenyldicarboxylate). 18. The method of claim 17, wherein the MOF comprises a repeating core of Co2(dobdc). 19. The method of claim 1, wherein the metal-metal separation distance of the MOF is from about 7.7 Å to about 12.7 Å. 20. The method of claim 10, wherein the MOF comprises 1-D hexagonal channels with a high density of 5-coordinate metal centers with a sixth, vacant coordination site pointing into the pores.
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