Interpenetrating Metal–Metalloporphyrin Framework for Selective CO<sub>2</sub> Uptake and Chemical Transformation of CO<sub>2</sub>

Gao, Wen; Tsai, Chen‐Yen; Wojtas, Łukasz; Thiounn, Timmy; Lin, Chu‐Chieh; Ma, Shengqian

doi:10.1021/acs.inorgchem.6b00937

Cited by 119 publications

(57 citation statements)

References 29 publications

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“…Based on the unique features of HMOFs as catalysts andt he above catalysis results, ap ossible cooperatively catalytic mechanism was proposed. [39][40][41][42][43][44][45][46] First, an epoxide is adsorbed and activatedb yt he Lewis acid dual metallicA g I and Tb III centers. Then, the ring-opening step is driven by the activation effect of the dual metallic Ag I and Tb III centers ites andt he epoxidei s attacked by the halogen ion on the less hindered side.…”

Section: Cycloaddition Of Co 2 With Epoxidesmentioning

confidence: 99%

Rational Stepwise Construction of Different Heterometallic–Organic Frameworks (HMOFs) for Highly Efficient CO₂ Conversion

Liu

Yang

et al. 2020

Chemistry A European J

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The coordination preference of different metal ions and ligandsh ave an immense influenceo nt he constructions of functional MOF materials.I nt his work, two new monometallicc omplexes,n amely [Ag(HL)(bipy) 0.5 ]( 1)a nd {[Tb(L) 1.5 (H 2 O)]·4H 2 O} n (2)( bipy = 4,4-bipyridine), have been synthesized successfully by employing abifunctional 2-(imidazol-1-yl)terephthalic acid (H 2 L) ligand.A fter that, two new different heterometallic-organic frameworks (HMOFs),were obtained from complexes 1 and 2 as the precursors based on ar ational stepwisec onstruction strategy and the theoryo fh ard and soft acids and bases (HSAB principle), respectively.T he HMOFs bearing dual metallic catalytic sites (Tb and Ag) can be used as heterogeneous catalysts without losing performance for the chemical fixation of CO 2 with epoxidesi ncluding the sterically hindered epoxides,d emonstratings ome of the highest reported catalytic activity values. This work may provideanew synthetic route toward tailoringnew HMOFs with excellent catalytic activity. Results and Discussion Structure descriptionSingle-crystal structure analysis reveals that complex 1 is ad iscrete monometallic molecule. It belongs to the monoclinic C2/ c space group, and itsa symmetricu nit consists of one Ag I ion, one HL À ligand, and half ab ipy molecule. The Ag I ion is linearly coordinatedw ith Na toms from HL À and bipy (Figure 1), the AgÀNb ond lengths are 2.105 and 2.131 ,r espectively.[a] J.

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Section: Cycloaddition Of Co 2 With Epoxidesmentioning

confidence: 99%

Rational Stepwise Construction of Different Heterometallic–Organic Frameworks (HMOFs) for Highly Efficient CO₂ Conversion

Liu

Yang

et al. 2020

Chemistry A European J

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“…Endowed with regulars tructures, high porosity,m odifiable porouss urface, metal-organic frameworks (MOFs) might be promisingp orous materials for selective gas adsorption and effective heterogeneousc atalysts, including the adsorption and separation of small moleculessuch as N 2 ,H 2 ,CO, and hydrocarbons (CH 4 and C 2 H 6 ) [9][10][11][12] as well as CO 2 adsorption and catalysis. [13][14][15][16][17][18] Recently,s ome excellent examples have witnessed the success of MOFs as heterogeneousc atalysts in the reaction of CO 2 with epoxides. [19,20] Wherein, the existence of accessible open metal sites (OMSs)a nd/ora cidic groupsi nt he pores are crucial for the catalytica ctivity of MOFs, which serve not only as CO 2 -binding sites but also as Lewis and/or Brønsted acidic catalytic sites.…”

Section: Introductionmentioning

confidence: 99%

An Uncommon Carboxyl‐Decorated Metal–Organic Framework with Selective Gas Adsorption and Catalytic Conversion of CO₂

Wang

Yang

et al. 2017

Chemistry A European J

115

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A new three-dimensional (3D) framework, [Ni(btzip)(H btzip)]⋅2 DMF⋅2 H O (1) (H btzip=4,6-bis(triazol-1-yl)isophthalic acid) as an acidic heterogeneous catalyst was constructed by the reaction of nickel wire and a triazolyl-carboxyl linker. Framework 1 possesses intersected 2D channels decorated by free COOH groups and uncoordinated triazolyl N atoms, leading to not only high CO and C H adsorption capacity but also significant selective capture for CO and C H over CH and CO in 273-333 K. Moreover, 1 reveals chemical stability toward water. Grand Canonical Monte Carlo simulations confirmed the multiple CO - and C H -philic sites. As a result of the presence of accessible Brønsted acidic COOH groups in the channels, the activated framework demonstrates highly efficient catalytic activity in the cycloaddition reaction of CO with propylene oxide/4-chloromethyl-1,3-dioxolan-2-one/3-butoxy-1,2-epoxypropane into cyclic carbonates.

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“…Up to now,s everal types of heterogeneousc atalysts have been developed, including metal oxides, [17] functional graphene oxide, [18] supportedc atalysts, [19] zeolitic imidazolate frameworks (ZIFs) and metal-organic frameworks (MOFs), [20][21][22][23][24][25][26][27] and porous organic polymers (POPs). [28][29][30][31][32][33][34] Recently,t he potential applicationso fP OPs in gas storage and separation, [35][36][37][38] energy transfer and conversions, [39,40] sensing, [41,42] and heterogeneous catalysis [28][29][30][31][32][33][34][43][44][45][46][47] were demonstrated.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of a Pyridine–Zinc‐Based Porous Organic Polymer for the Co‐catalyst‐Free Cycloaddition of Epoxides

Chen

et al. 2017

Chemistry An Asian Journal

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The synthesis of solid catalysts for the co-catalyst-free cycloaddition of CO has attracted much attention. Herein, we report a hierarchical porous organic polymer, Py-Zn@MA, that is able to catalyze the cycloaddition reaction of epoxides and CO without using any additives or co-catalyst to afford turnover frequency (TOF) values as high as 250 and 97 h at 130 °C by using pure and diluted CO (simulating flue gas), respectively. These results are superior to those obtained from previously reported heterogeneous co-catalyst-free systems. The high activity of Py-Zn@MA is mainly attributed to its bifunctional nature with ZnBr and pyridine activating the epoxide in a cooperative way. Notably, Py-Zn@MA can be easily prepared on a large scale without using any catalyst and the chemicals are cost effective. Moreover, Py-Zn@MA shows good substrate universality for the cycloaddition reactions of epoxides. Our designed porous organic polymer Py-Zn@MA material has the potential to serve as an efficient catalyst for the direct conversion of flue gas with epoxides into value-added cyclic carbonates.

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Interpenetrating Metal–Metalloporphyrin Framework for Selective CO₂ Uptake and Chemical Transformation of CO₂

Cited by 119 publications

References 29 publications

Rational Stepwise Construction of Different Heterometallic–Organic Frameworks (HMOFs) for Highly Efficient CO₂ Conversion

Rational Stepwise Construction of Different Heterometallic–Organic Frameworks (HMOFs) for Highly Efficient CO₂ Conversion

An Uncommon Carboxyl‐Decorated Metal–Organic Framework with Selective Gas Adsorption and Catalytic Conversion of CO₂

Synthesis of a Pyridine–Zinc‐Based Porous Organic Polymer for the Co‐catalyst‐Free Cycloaddition of Epoxides

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Interpenetrating Metal–Metalloporphyrin Framework for Selective CO2 Uptake and Chemical Transformation of CO2

Cited by 119 publications

References 29 publications

Rational Stepwise Construction of Different Heterometallic–Organic Frameworks (HMOFs) for Highly Efficient CO2 Conversion

Rational Stepwise Construction of Different Heterometallic–Organic Frameworks (HMOFs) for Highly Efficient CO2 Conversion

An Uncommon Carboxyl‐Decorated Metal–Organic Framework with Selective Gas Adsorption and Catalytic Conversion of CO2

Synthesis of a Pyridine–Zinc‐Based Porous Organic Polymer for the Co‐catalyst‐Free Cycloaddition of Epoxides

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Product

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Interpenetrating Metal–Metalloporphyrin Framework for Selective CO₂ Uptake and Chemical Transformation of CO₂

Rational Stepwise Construction of Different Heterometallic–Organic Frameworks (HMOFs) for Highly Efficient CO₂ Conversion

Rational Stepwise Construction of Different Heterometallic–Organic Frameworks (HMOFs) for Highly Efficient CO₂ Conversion

An Uncommon Carboxyl‐Decorated Metal–Organic Framework with Selective Gas Adsorption and Catalytic Conversion of CO₂