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Letter
Unusual Missing Linkers in Organosulfonate-Based pcu-Type Metal-Organic Frameworks for CO2 Capture and Conversion Under Ambient Condition Guiyang Zhang, Huimin Yang, and Honghan Fei ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.7b04189 • Publication Date (Web): 13 Feb 2018 Downloaded from http://pubs.acs.org on February 14, 2018
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ACS Catalysis
Unusual Missing Linkers in Organosulfonate-Based pcu-Type MetalOrganic Frameworks for CO 2 Capture and Conversion Under Ambient Condition Guiyang Zhang, Huimin Yang, and Honghan Fei* Shanghai Key Laboratory of Chemical Assessment and Sustainability, School of Chemical Science and Engineering, Tongji University, Shanghai 200092, P. R. China ABSTRACT: A non-interpenetrated organosulfonate-based metal-organic framework (MOF) with a defective pcu topology was successfully synthesized. The unusual missing linkers along with the highest permanent porosity (~43 %) in sulfonate-MOFs offer a versatile platform for incorporation of alkynophilic Ag(I) sites. The cyclic carboxylation of alkyne molecules (e.g. propargyl alcohol and propargyl amine) into α-alkylidene cyclic carbonates and oxazolidinones were successfully catalyzed by the use of Ag(I)-embedded sulfonate-MOF under atmospheric pressure of CO 2 . In all the three catalytic reactions using CO 2 as a C1 feedstock, the highly robust sulfonate-based MOF catalyst exhibit at least three-cycle reusability. KEYWORDS: metal-organic frameworks, sulfonate, CO 2 fixation, heterogeneous catalysis, alkyne activation
Carbon dioxide (CO 2 ), the anthropogenically emitted gas, has become a widely recognized issue for global warming and subsequent environmental problems.1,2 Transformation of CO 2 to high-value chemicals is an emerging strategy to utilize CO 2 as a renewable C1 resource,3-5 although CO 2 is the most thermodynamically stable state in carbon derivatives. The cyclization of unsaturated organic molecules via CO 2 is an atom-economic and environmental benign approach to and produce α-alkylidene cyclic carbonates6,7 8,9 oxazolidinones, which are the essential building blocks for plastics10 and antibiotics,11 respectively. However, precious transition-metal catalyzed processes are often not heterogeneous and/or require harsh conditions (e.g. high temperature and CO 2 pressure) to perform the carboxylative cyclization.3 Thus, it is challenging and imperative to discover highly robust catalysts to achieve the conversion under ambient conditions (ideally at 1 bar and room temperature) in an environmental friendly and recyclable manner. Metal-organic frameworks (MOFs) are an emerging class of functionalized solid-state catalysts, owing to their siteisolated catalytic sites, well-defined porosity, versatile functionalities, and great reusability.12-14 Moreover, MOFs are developed to be one of the most efficient and promising CO 2 adsorbents,15-18 thus significantly enhancing the local concentration of CO 2 near the catalytic sites for its conversion. Up-to-date, the vast majority of MOF-based catalysts for organic transformations of CO 2 were largely limited to the cycloaddition of CO 2 with epoxides (or aziridines), while the three-membered epoxide is a very high-energy starting material.19-24 Moreover, the co-catalyst (e.g. n-Bu 4 NBr) plays a significant role in the reaction and performs turnover by itself, thus many mechanistic details need to be addressed.25 An alternate strategy to use CO 2 as a C1 feedstock in organic synthesis is the carboxylation of terminal alkyne molecules.26 The only two successful MOF-related examples are either not completely recyclable or using MOF as a host for
encapsulating catalytic species.27,28 Very recently, Duan and co-workers reported a Ag(I)-based MOF catalyzing the carboxylative cyclization of propargyl alcohols with CO 2 , though in need of elevated temperature and pressure (50°C, 5 bar).29 Reticular engineering of MOF architectures is closely related to the prominent metal-carboxylate secondary building units, which result in the nonpolar porosity of the unfunctionalized carboxylate-based MOFs.30-33 In contrast, the versatile metal-sulfonate coordination modes are promising to achieve rich architectures of organosulfonatebased MOFs with high polar porosity and inherent metal/linker vacancies.33,34 However, hard metal centers usually prefer the aqua-ligands over sulfonates, thus affording dense zero- or one-dimensional structures.35,36 Recently, we employed a mixed-linker strategy to construct threedimensional (3D) porous organosulfonate-based MOFs possessing a prototypical primitive-cubic (pcu) topology.37,38 On the other hand, defect engineering in MOFs is a phenomenal concept that the metal or linker vacancies provide potentially active sites for gas sorption and catalysis.39 Herein, we discover a non-interpenetrated sulfonatebased porous MOF with a prototypical pcu topology. Moreover, the defective, porous topology possesses unusual ligand vacancies in an ordered fashion, affording an array of linker-pendant sulfonate groups for Ag(I) metalation. The synergistic effect of high CO 2 affinity and alkyne activation enables the Ag(I)-decorated sulfonate-MOF to be an efficient catalyst for cyclization of alkyne and CO 2 , affording αalkylidene cyclic carbonates and oxazolidinones with high yields under ambient condition. Importantly, this is a MOF catalyst to perform all of the three CO 2 -based carboxylative cyclization reactions for at lease three cycles under atmospheric pressure and room temperature, attributable to its precisely functionalized porosity and high robustness.
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Figure 1. a) Scheme of TMOF-3 synthesis; b) crystallographic view of TMOF3 along b axis and 4,4’-bipyridines are simplified as rods for clarity; c) topological view of TMOF-3 with the uncoordinated sulfonate groups highlighted (Cu green, O red, S yellow).
The multitopic 1,2,4,5-benzenetetramethanesulfonate (1,2,4,5-BTMS) ligand was obtained in high yield (>90%) by the substitution reaction of 1,2,4,5tetrakis(bromomethyl)benzene with sodium sulfite (see ESI, Scheme S1). Hydrothermal reaction of Cu(NO 3 ) 2 , 1,2,4,5BTMS, and 4,4’-bipyridine (bpy) afforded dark-blue block crystals of [Cu(bpy) 2 (1,2,4,5-BTMS) 0.5 (H 2 O) 0.5 ] n (Figure S2), which we denote as TMOF-3 (TMOF=Tongji MOF). X-ray crystallography reveals TMOF-3 is crystallized in a monoclinic space group of C2/c. The overall structure occupies a prototypical, non-interpenetrated pcu-net topology with an “I0O3” connectivity, using Cheetham et. al.’s proposed nomenclature (Figure 1).40 The pcu network can be viewed as single Cu2+ atoms connected in three dimensions with the organic struts of bpy and 1,2,4,5-BTMS. Each 1,2,4,5-BTMS ligand has only two para-positioned sulfonate groups forming coordination bonds (RO 2 S-O···Cu) with Cu2+ nodes, presenting as the pillars for the adjacent (4,4)-connected bricklike [Cu(bpy) 2 ] n 2n+ layers. The other two sulfonate functional groups are deprotonated and dangling in the cavity of the pcu net (Figure 1b and 1c), suggested by the overall charge compensation based on X-ray crystallography as well as fourier-transformed infrared spectroscopy (FTIR) (Figure S3). Importantly, 50% of the 1,2,4,5-BTMS ligands are missing in the defective pcu net, and the overall linker vacancies of the total organic linkers in TMOF-3 reach up to one-sixth (16.7%). The presence of the unusual ligand vacancies is probably owing to the steric effect of the tetratopic 1,2,4,5-BTMS as well as the competing coordinating tendencies between aqua-ligands and sulfonates. The coordination spheres of the defective Cu2+ centers are completed by two weakly-bound water molecules in the axial positions with a long contact distance of 2.45 Å (Figure 2).
Figure 2. Coordination environment of the Cu(II) centers in TMOF-3 (Cu green, O red, S yellow, C grey, N blue).
Overall, TMOF-3 is a non-interpenetrated organosulfonate-based MOF with a pcu-type topology, and possesses the highest void space (42.5% by PLATON calculations)41 among MOFs containing an organosulfonate linker. Moreover, its high yield and phase purity are
evidenced by experimental powder X-ray diffraction (PXRD), which matches well with theoretical pattern simulated from the crystallographic studies (Figure 3). Despite occupying a defective pcu network, TMOF-3 demonstrates a high chemical robustness over a wide pH range from 3 to 10, as well as the aqueous condition. After incubating the isolated TMOF-3 crystals in water, diluted HCl solution (pH=3) and diluted NaOH solution (pH=10) for 24 h, no significant loss of crystallinity was observed in PXRD patterns as well as BET surface areas (Figure 3 and Figure S5). The water-stable nature of TMOF-3 is probably ascribed to the Cu(II) centers occupying an energetically-stable Jahn-Teller distorted octahedral geometry, thus less susceptible to hydrolysis and outperforming the vast majority of carboxylate-based MOFs with a pcu topology.42
Figure 3. PXRD patterns of TMOF-3/TMOF-3-Ag before and after chemical treatment.
Successful activation of TMOF-3 was performed by incubation of the solids in fresh methanol solution, followed by high-vacuum activation at room temperature for overnight. The nature of permanent porosity and the retention of pcu topology were demonstrated by the agreement of the PXRD between the activated sample and simulated data from singlecrystal data (Figure S6). The activated TMOF-3 exhibited a Brunauer-Emmett-Teller (BET) surface area of 870 m2/g with a reversible type I sorption isotherm measured by N 2 adsorption at 77K, demonstrating its microporous nature (Figure 4a and Figure S7). Since the vast array of strongly polar sulfonate groups (both coordinated and dangling) would have a high affinity towards CO 2 , TMOF-3 showed a high CO 2 uptake of 102 cm3/g (20.0 wt.%) at 273 K and 74 cm3/g (14.5 wt.%) at 298 K under 1 bar. To the best of our knowledge, these numbers are not only the highest in all of the organosulfonate-based MOFs,37,38,43 but among the best performances in the low-pressure CO 2 adsorption capacities for functionalized carboxylate-based MOFs. The zerocoverage isosteric heat of adsorption (Q st ) of TMOF-3 was calculated to be 29.2 kJ/mol, further confirming the strong affinity of TMOF-3 to CO 2 . Indeed, TMOF-3 demonstrated a rather steep increase at low pressure in H 2 sorption isotherms (77 K and 87 K) and a Q st of 9.0 kJ/mol (Figure S8), which is probably due to the coordinatively unsaturated Cu(II) sites residing in activated TMOF-3. The high porosity and the immobilized, linkerpendant sulfonate groups on TMOF-3 provide an excellent platform to introduce a second metal center, such as alkynophilic Ag(I) sites. Successful Ag(I)-metalation was performed by incubating ~120 mg activated sample of TMOF3 in 10 mL AgNO 3 aqueous solution (10 mmol/L) and fixed onto a shaker (IKA KS 3000) with a shaking rate of 100 cpm
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ACS Catalysis for 1 h, affording the resulting TMOF-3-Ag (Figure 5a). Inductively coupled plasma optical emission spectra (ICPOES) revealed an atomic ratio of 1:(5.8±0.3) (Ag:Cu) in the Ag(I)-decorated TMOF-3, confirming ~17% of the free sulfonate sites were metalated. X-ray photoelectron spectrum (XPS) indicated a characteristic binding energy of Ag(I) (368.1 and 374.2 eV) in TMOF-3-Ag, which is comparable with CH 3 SO 3 Ag (368.3 and 374.3 eV) (Figure S9). Moreover, transmission electron microscopy (TEM) images exhibited no deposition of Ag nanoparticles on the crystal surface (Figure S10). ICP-OES of the Ag(I)-metalation supernatant showed no leaching of Cu from TMOF-3, excluding the possibility of cation exchange process. In addition, the nearest distance between two dangling sulfonate groups is ~6.6 Å, which is obviously too long to chelate a single Ag(I) ion. These experiments suggest the formation of AgO 3 S-R moieties in TMOF-3-Ag. The high crystallinity of TMOF-3 was well retained throughout the metalation, as evidenced by PXRD and the resulting dark-blue crystals (Figure 3). Indeed, a high water stability and an expected decrease in BET surface area (627 m2/g) were observed for TMOF-3-Ag (Figure 3 and Figure 4a).
Figure 4. a) N 2 adsorption-desorption isotherms at 77K, TMOF-3 black, TMOF-3-Ag blue; b) CO 2 adsorption-desorption isotherms of TMOF-3, 273K black, 298K blue.
Since silver complexes are known to have both σcomplexation and π-complexation properties with terminal alkynes,44,45 we used the gas adsorption and FTIR to examine the activation of C≡C bonds by TMOF-3-Ag. The lowpressure acetylene sorption isotherms of TMOF-3-Ag show the high acetylene uptake capacity of 103 cm3/g (12.0 wt.%) at 273 K and 75 cm3/g (8.7 wt.%) at 298 K, substantially surpassing its ethane uptake capacity under the identical condition (Figure 5b). Moreover, the Q st of acetylene for TMOF-3-Ag is calculated to be 34.2 kJ/mol, which is significantly higher than TMOF-3 (before Ag decoration) as well as some reported high acetylene-uptake MOFs with open metal sites (Figure S11-S13).46,47 In order to further confirm the complexation and activation of alkyne-containing molecules via Ag(I) sites residing in TMOF-3-Ag, we employed FTIR to characterize both MOFs (before and after Ag(I) decoration) that are treated with 2-methyl-3-butyn-2-ol (a). The propargyl alcohol substrate is chosen due to it presenting as the precursor for chemical CO 2 fixation that will be discussed later. After extensive washing with fresh ethanol, the new and distinct peaks appear at 2111 cm-1 and 3295 cm-1 for both MOFs that are characteristic of C≡C stretching and ≡C-H stretching, respectively (Figure 5c and Figure S14). These results confirm the successful inclusion of the propargyl alcohol molecules inside the porosity of TMOF-3 and TMOF3-Ag. More importantly, the obvious blue-shifted bands at 2162 cm-1 and 3326 cm-1 were observed in propargyl alcoholtreated TMOF-3-Ag (Figure 5c and Figure S14), clearly suggesting the complexation and activation of the terminal alkyne moieties within the pores of TMOF-3-Ag.44,48
Figure 5. a) Scheme representation of the Ag(I) metalation for TMOF-3, ligands are simplified as rods for clarity; b) ethane and acetylene sorption of TMOF-3-Ag; c) FTIR spectra of 2-methyl-3-butyn-2-ol (a) (black), TMOF-3 before (blue) and after (red) treating with a, and TMOF-3-Ag before (cyan) and after (magenta) treating with a.
Given the synergistic nature of the high CO 2 affinity and alkyne activation from TMOF-3-Ag, we sought to investigate its catalytic activity in carboxylative cyclization of propargyl alcohol with CO 2 . The cyclization of unsaturated 2methyl-3-butyn-2-ol to produce α-alkylidene cyclic carbonates was carried out under very mild condition (1 atm CO 2 and room temperature), and 1,8-diazabicyclo-[5.4.0]underc-7-ene (DBU) was proven to be an efficient base for this type of carboxylation reactions.49,50 Using TMOF-3-Ag (10 mol% in Ag), quantitative yield of the targeted α-alkylidene cyclic carbonate product was achieved in 6 h. Meanwhile, TMOF-3 before Ag decoration gave no conversion, evidencing the catalytically active Ag(I) sites. Despite the homogeneous AgNO 3 completed the reaction under the same condition, our MOF catalyst exhibits excellent recyclability without an obvious decrease in both yields and kinetics over three catalytic cycles (Figure S16a). The crystalline TMOF-3-Ag could be simply recovered by filtration, washed with ethanol, dried under vacuum, and then directed used for additional cycles. The post-catalysis TMOF-3-Ag exhibited no change in oxidation state and coordination environment of the Ag(I) catalytic sites despite the decreased crystallinity, evidenced by PXRD, XPS and TEM (Figure S9, S10 and S17). The heterogeneous nature of TMOF-3-Ag was further confirmed by a hot filtration of the catalyst after the first hour of the reaction, which resulted in negligible additional yield up to 5 h after filtration (Figure S18). Moreover, no leaching of metal species was detected by ICP-OES, showing the presence of merely 0.3 ppm Ag and 0.1 ppm Cu in the reaction solution. These experiments suggest that TMOF-3-Ag is a true heterogeneous catalyst. Importantly, this is one of the few example to catalyze the carboxylative cyclization of propargyl alcohol under ambient condition (1 atm CO 2 , room temperature) using MOF materials. To note, the high activity of our TMOF-3-Ag gives quantitative yields using merely 10 mol% co-catalyst (DBU), while other homogeneous or heterogeneous catalyst often require a stoichiometric amount of the toxic/costly base or high pressure of CO 2 (Table S2). Seven propargyl alcohols were used as substrates to synthesize the α-alkylidene cyclic carbonates (Table 1). Among them, the majority of the unsaturated molecules gave a nearly quantitative yield. Meanwhile, the internal propargyl alcohol affords the corresponding carbonate in 25(5) % yield, probably due to its steric hindrance to diffuse into the MOF porosity as well as
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the insufficient π-activation of Ag(I) sites towards internal alkyne moieties (Figure S16). Table 1. Carboxylic cyclization of propargylic alcohol with CO 2 .[a] O R1 R3
(0.1MPa) + OH CO2
catalyst, DBU
R2
DMF, r.t.
O R1
O R2
R3
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pressure. Notably, TMOF-3-Ag can be easily recovered after the reaction, and then directly used for additional cycles with yields over 90% (Figure S20). Moreover, six oxazolidinones were obtained successfully using different propargyl alcohol and primary amines substrates, which likely involves the mechanism of tandem aminolysis of α-alkylidene cyclic carbonates followed by intramolecular cyclization (Figure S21).51 Table 3. Three-component carboxylic cyclization of propargyl alcohol, CO 2 and primary amine.[a] O R1 OH
+ R NH + CO (0.1MPa) 2 2 3
R2
Product O
[a] Reaction conditions: 0.2 mmol propargylic alcohol, 10 mol% TMOF-3-Ag (based on Ag) along with 0.1 eq. DBU, 2 mL DMF, 0.1 MPa CO 2 atmosphere, room temperature, 6 hours; [b] yields determined by 1H-NMR, an average value of three runs (error in parentheses).
1
O
2
O
3
O
4
O
5
O
N
O N
O
The high catalytic activity of TMOF-3-Ag toward the carboxylic cyclization of propargylic alcohols is largely ascribed to the fast mass-transport from the high surface area as well as the highly robust nature of the pcu topology. In contrast, the catalytic activity of the heterogeneous Ag(I) salts is strongly interfered due to the low accessibility of the metal sites and the limited reaction rate by mass transport. The control reaction between 2-methyl-3-butyn-2-ol with CO 2 catalyzed by a series of Ag(I) salts afforded rather low yields of the targeted products as expected (Table 2).
N
O N
Catalyst 1 2 3 4 5 6 7 8
AgCl AgBr AgI Ag 2 CO 3 Ag 2 SO 4 Ag 2 S TMOF-3 TMOF-3-Ag
Time (h) 6 6 6 6 6 6 6 6
Yield (%)[b] 9(2) 29(3) 26(2) 8(2) 46(3) 99
[a] Reaction conditions: 0.2 mmol 2-methyl-3-butyn-2-ol, 10 mol% catalyst along with 0.1 eq. DBU, 2 mL DMF, 0.1 MPa CO 2 atmosphere, room temperature; [b] yields determined by 1H-NMR, an average value of three runs (error in parentheses).
Since oxazolidinones are an important building block for antibiotics, we employed a three-component reaction between propargyl alcohol, CO 2 and primary amine to afford the corresponding carbamates (Table 3). The atom-economic synthetic strategy catalyzed by a heterogeneous MOF-based catalyst may achieve the completely “green” chemistry process. Importantly, the transformation between a, CO 2 and n-propylamine was performed to reach nearly quantitative yield with the catalyst of TMOF-3-Ag under extremely mild condition (1 atm CO 2 and 50 oC) after 12h (Figure S19). To the best of our knowledge, this is a rare example to achieve this three-component catalytic process at atmospheric CO 2
o
DMSO, 50 C
O R1
N
R3
R2
mol%
Time
Yield
(Ag)
(h)
(%)[b]
n-Pr
TMOF-3-Ag
10
6
65(2)
TMOF-3-Ag
10
12
97(2)
TMOF-3
0[c]
12
0
TMOF-3-Ag
10
12
>99
TMOF-3-Ag
10
12
>99
TMOF-3-Ag
10
12
>99
TMOF-3-Ag
10
12
>99
TMOF-3-Ag
10
12
>99
n-Pr
n-Pr
n-Bu
O i-Pr
N
O
6
O
7
O
N
O
Table 2. Carboxylic cyclization of 2-methyl-3-butyn-2-ol with CO 2 using heterogeneous Ag(I)-based catalysts.[a]
Catalyst
catalyst, Ph3P
N
n-Pr
C 2H 5 O
8
O
N
n-Bu
C 2H 5
[a] Reaction conditions: 0.2 mmol propargylic alcohol, 0.2 mmol primary amine, certain amount of catalyst (based on Ag), 10 mol% Ph 3 P, 2 mL DMSO, 0.1 MPa CO 2 atmosphere, 50 oC; [b] yields determined by 1H-NMR, an average value of three runs (error in parentheses); [c] equal mol% of MOF as entry 1.
Following the above three-component catalysis results, we further establish a catalytic protocol to afford oxazolidinones between propargyl amine and CO 2 . Five different propargyl amine were synthesized according to literature,52 and the cyclic carboxylation with CO 2 afforded the targeted carbamate product smoothly with high yields in the presence of 10 mol% DBU and 10 mol% TMOF-3-Ag under 1 atm CO 2 (Table 4, Figure S22). Control experiments of TMOF-3 and AgNO 3 revealed that embedded Ag(I) are the true active sites, which undergo the mechanism that the silvercoordinated propargyl amine reacts with CO 2 -trapped DBU to afford the product by CO 2 transfer (Figure S23). Again, the recyclability experiments were performed using the same batch of 10 mol% TMOF-3-Ag over 3 cycles without a decrease in yield of the targeted oxazolidinone (Figure S24). Table 4. Carboxylic cyclization of propargyl amine with CO 2 .[a] O R3
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H N R2
+ CO (0.1MPa)
R1
2
TMOF-3-Ag, DBU
O
o
DMSO, 50 C
R3
N
R1 R2
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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
O
O N
PMB O
O N
O
Bn
N
O
Bn O
O N
Bn
O
N
Bn
(7) >99 %[b, c]
>99 %
>99 %
89(2) %
96(2) %
[a] Reaction conditions: 0.2 mmol propargyl amine, 0.1 eq. TMOF-3-Ag (based on Ag) along with 0.1 eq. DBU, 2 mL DMF, 0.1 MPa CO 2 atmosphere, room temperature, six hours; [b] yields determined by 1H-NMR, an average value of three runs (error in parentheses); [c] PMB = p-methoxybenzyl.
In conclusion, we synthesized a non-interpenetrated pcu-type sulfonate-based metal-organic framework, and the unusual linker-defective nature allows for the subsequent incorporation of Ag(I) active sites. The chemically robust TMOF-3-Ag(I) occupies both the high CO 2 affinity from the sulfonate functionality and the alkyne activation nature from the embedded Ag(I) sites, providing an excellent platform for cyclic carboxylation of alkyne molecules and CO 2 . The catalysis presented here achieves efficient and recyclable cyclic carboxylation of terminal alkyne substrates and CO 2 under very mild condition (1 atm CO 2 and low temperature) using MOF catalysts. This work reveals the potential applications of inherently high-polarity pore surface in functionalized and permanently porous sulfonate-based MOFs for CO 2 capture and sequestration technologies.
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AUTHOR INFORMATION Corresponding Author *E-mail:
[email protected] (16)
Notes
The authors declare no competing financial interest.
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ASSOCIATED CONTENT Supporting Information. Detailed experimental procedures, additional characterization figures and tables. This material is available free of charge via the Internet at http://pubs.acs.org.
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ACKNOWLEDGMENT This work was supported by grants from the National Natural Science Foundation of China (51772217, 21501136), the Recruitment of Global Youth Experts by China, the Fundamental Research Funds for the Central Universities, and the Science & Technology Commission of Shanghai Municipality (14DZ2261100).
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