Global investment in counteracting climate change has galvanized increasing interest in carbon ca... more Global investment in counteracting climate change has galvanized increasing interest in carbon capture and sequestration (CCS) as a versatile emissions mitigation technology. As decarbonization efforts accelerate, CCS can target the emissions of large point-source emitters, such as coal- or natural gas-fired power plants, while also supporting the production of renewable or low-carbon fuels. Furthermore, CCS can enable decarbonization of difficult-to-abate industrial processes and can support net CO2 removal from the atmosphere through bioenergy coupled with CCS or direct air capture. Here we review the development of porous materials as next-generation sorbents for CO2 capture applications. We focus on stream- and sector-specific challenges while highlighting case studies within the context of the rapidly shifting energy landscape. We conclude with a discussion of key needs from the materials community to expand deployment of carbon capture technologies. Porous materials can selectively and reversibly adsorb large quantities of gas. This Review highlights progress made in using this class of materials for CO2 capture processes and discusses key gaps that the materials community can address to accelerate greater adoption of adsorptive carbon capture technologies.
Journal of the American Chemical Society, May 20, 2016
A new metal-organic framework, Fe-BTTri (Fe3[(Fe4Cl)3(BTTri)8]2·18CH3OH, H3BTTri =1,3,5-tris(1H-1... more A new metal-organic framework, Fe-BTTri (Fe3[(Fe4Cl)3(BTTri)8]2·18CH3OH, H3BTTri =1,3,5-tris(1H-1,2,3-triazol-5-yl)benzene)), is found to be highly selective in the adsorption of CO over a variety of other gas molecules, making it extremely effective, for example, in the removal of trace CO from mixtures with H2, N2, and CH4. This framework not only displays significant CO adsorption capacity at very low pressures (1.45 mmol/g at just 100 μbar), but, importantly, also exhibits readily reversible CO binding. Fe-BTTri utilizes a unique spin state change mechanism to bind CO in which the coordinatively unsaturated, high-spin Fe(II) centers of the framework convert to octahedral, low-spin Fe(II) centers upon CO coordination. Desorption of CO converts the Fe(II) sites back to a high-spin ground state, enabling the facile regeneration and recyclability of the material. This spin state change is supported by characterization via infrared spectroscopy, single crystal X-ray analysis, Mössbau...
Reaction of [(cyclen)V(CF(3)SO(3))(2)](CF(3)SO(3)) with 4 equiv. of Et(4)N(CN) in DMF generates t... more Reaction of [(cyclen)V(CF(3)SO(3))(2)](CF(3)SO(3)) with 4 equiv. of Et(4)N(CN) in DMF generates the seven-coordinate complex [(cyclen)V(CN)(3)], while a reaction employing just 1.5 equiv. produces a tetrahedral cage complex, [(cyclen)(4)V(4)(CN)(6)](6+), in which antiferromagnetic coupling leads to an S= 0 ground state.
Combining porosity and magnetic ordering in a single material presents a significant challenge si... more Combining porosity and magnetic ordering in a single material presents a significant challenge since magnetic exchange generally requires short bridges between the spin carriers, whereas porosity usually relies on the use of long diamagnetic connecting ligands. Despite this apparent incompatibility, notable successes have been achieved of late in generating truly microporous solids with high magnetic ordering temperatures. In this critical review, we give an overview of this emerging class of multifunctional materials, with particular emphasis on synthetic strategies and possible routes to new materials with improved properties (149 references).
In nature, nonheme iron enzymes use dioxygen to generate high-spin iron(IV)=O species for a varie... more In nature, nonheme iron enzymes use dioxygen to generate high-spin iron(IV)=O species for a variety of oxygenation reactions. Although synthetic chemists have long sought to mimic this reactivity, the enzyme-like activation of O 2 to form high-spin iron(IV) = O species remains an unrealized goal. Here, we report a metal–organic framework featuring iron(II) sites with a local structure similar to that in α-ketoglutarate-dependent dioxygenases. The framework reacts with O 2 at low temperatures to form high-spin iron(IV) = O species that are characterized using in situ diffuse reflectance infrared Fourier transform, in situ and variable-field Mössbauer, Fe Kβ x-ray emission, and nuclear resonance vibrational spectroscopies. In the presence of O 2 , the framework is competent for catalytic oxygenation of cyclohexane and the stoichiometric conversion of ethane to ethanol.
The extraordinarily rich chemistry of octahedral transition metal halide and chalcohalide cluster... more The extraordinarily rich chemistry of octahedral transition metal halide and chalcohalide clusters has begun to see use in a variety of applications, ranging from catalysis to chemical sensing. In facilitating the design of such cluster-based materials, new synthetic methods for adjusting the core electronic character by atom substitution and for exchanging the six outer terminal ligands are of considerable value. However, the prospect of utilizing a wholly different type of cluster unit arose very recently with the discovery of the molecular species [W6CCl18] n (n = 0–3). Instead of an octahedron, these clusters feature a carbon-centered W6 trigonal prism surrounded by twelve edge-bridging chloride anions and six radially extended terminal chloride ligands. Such units are also known to exist within the one-dimensional compounds A3Nb6SBr17 (A = K, Rb, Cs, and Tl), [4] suggesting that this trigonal-prism structure type may be quite pervasive. Noting that the electronic character of t...
One-step purification and desalination The purification of water for drinking purposes can requir... more One-step purification and desalination The purification of water for drinking purposes can require multiple filtration steps and technologies to remove contaminants such as salts and heavy metals. Some contaminants could have value if recovered, but these are often discharged in the waste streams. Uliana et al. describe a general approach for the fabrication of robust, tunable, adsorptive membranes through the incorporation of porous aromatic framework (PAF) nanoparticles into ion exchange membranes such as those made from sulfonated polymers. Salts are removed using a series of cation and anion exchange membranes, and the PAF particles can be selected to capture specific target ions, such as those of copper, mercury, or iron. This allows for simultaneous desalination and decontamination of the water. Science , this issue p. 296
Advanced materials (Deerfield Beach, Fla.), Jan 8, 2018
Many forward-looking clean-energy technologies hinge on the development of scalable and efficient... more Many forward-looking clean-energy technologies hinge on the development of scalable and efficient membrane-based separations. Ongoing investment in the basic research of microporous materials is beginning to pay dividends in membrane technology maturation. Specifically, improvements in membrane selectivity, permeability, and durability are being leveraged for more efficient carbon capture, desalination, and energy storage, and the market adoption of membranes in those areas appears to be on the horizon. Herein, an overview of the microporous materials chemistry driving advanced membrane development, the clean-energy separations employing them, and the theoretical underpinnings tying membrane performance to membrane structure across multiple length scales is provided. The interplay of pore architecture and chemistry for a given set of analytes emerges as a critical design consideration dictating mass transport outcomes. Opportunities and outstanding challenges in the field are also d...
Angewandte Chemie (International ed. in English), Jan 11, 2017
Hexakis(2,6-diisopropylphenylisocyanide)tantalum is the first isocyanide analogue of the highly u... more Hexakis(2,6-diisopropylphenylisocyanide)tantalum is the first isocyanide analogue of the highly unstable Ta(CO)6 and represents the only well-defined zerovalent tantalum complex to be prepared by conventional laboratory methods. Two prior examples of homoleptic Ta(0) complexes are known, Ta(benzene)2 and Ta(dmpe)3 , dmpe=1,2-bis(dimethylphosphano)ethane, but these have only been accessed via ligand co-condensation with tantalum vapor in a sophisticated metal-atom reactor. Consistent with its 17-electron nature, Ta(CNDipp)6 undergoes facile one-electron oxidation, reduction, or disproportionation reactions. In this sense, it qualitatively resembles V(CO)6 , the only paramagnetic homoleptic metal carbonyl isolable under ambient conditions.
Global investment in counteracting climate change has galvanized increasing interest in carbon ca... more Global investment in counteracting climate change has galvanized increasing interest in carbon capture and sequestration (CCS) as a versatile emissions mitigation technology. As decarbonization efforts accelerate, CCS can target the emissions of large point-source emitters, such as coal- or natural gas-fired power plants, while also supporting the production of renewable or low-carbon fuels. Furthermore, CCS can enable decarbonization of difficult-to-abate industrial processes and can support net CO2 removal from the atmosphere through bioenergy coupled with CCS or direct air capture. Here we review the development of porous materials as next-generation sorbents for CO2 capture applications. We focus on stream- and sector-specific challenges while highlighting case studies within the context of the rapidly shifting energy landscape. We conclude with a discussion of key needs from the materials community to expand deployment of carbon capture technologies. Porous materials can selectively and reversibly adsorb large quantities of gas. This Review highlights progress made in using this class of materials for CO2 capture processes and discusses key gaps that the materials community can address to accelerate greater adoption of adsorptive carbon capture technologies.
Journal of the American Chemical Society, May 20, 2016
A new metal-organic framework, Fe-BTTri (Fe3[(Fe4Cl)3(BTTri)8]2·18CH3OH, H3BTTri =1,3,5-tris(1H-1... more A new metal-organic framework, Fe-BTTri (Fe3[(Fe4Cl)3(BTTri)8]2·18CH3OH, H3BTTri =1,3,5-tris(1H-1,2,3-triazol-5-yl)benzene)), is found to be highly selective in the adsorption of CO over a variety of other gas molecules, making it extremely effective, for example, in the removal of trace CO from mixtures with H2, N2, and CH4. This framework not only displays significant CO adsorption capacity at very low pressures (1.45 mmol/g at just 100 μbar), but, importantly, also exhibits readily reversible CO binding. Fe-BTTri utilizes a unique spin state change mechanism to bind CO in which the coordinatively unsaturated, high-spin Fe(II) centers of the framework convert to octahedral, low-spin Fe(II) centers upon CO coordination. Desorption of CO converts the Fe(II) sites back to a high-spin ground state, enabling the facile regeneration and recyclability of the material. This spin state change is supported by characterization via infrared spectroscopy, single crystal X-ray analysis, Mössbau...
Reaction of [(cyclen)V(CF(3)SO(3))(2)](CF(3)SO(3)) with 4 equiv. of Et(4)N(CN) in DMF generates t... more Reaction of [(cyclen)V(CF(3)SO(3))(2)](CF(3)SO(3)) with 4 equiv. of Et(4)N(CN) in DMF generates the seven-coordinate complex [(cyclen)V(CN)(3)], while a reaction employing just 1.5 equiv. produces a tetrahedral cage complex, [(cyclen)(4)V(4)(CN)(6)](6+), in which antiferromagnetic coupling leads to an S= 0 ground state.
Combining porosity and magnetic ordering in a single material presents a significant challenge si... more Combining porosity and magnetic ordering in a single material presents a significant challenge since magnetic exchange generally requires short bridges between the spin carriers, whereas porosity usually relies on the use of long diamagnetic connecting ligands. Despite this apparent incompatibility, notable successes have been achieved of late in generating truly microporous solids with high magnetic ordering temperatures. In this critical review, we give an overview of this emerging class of multifunctional materials, with particular emphasis on synthetic strategies and possible routes to new materials with improved properties (149 references).
In nature, nonheme iron enzymes use dioxygen to generate high-spin iron(IV)=O species for a varie... more In nature, nonheme iron enzymes use dioxygen to generate high-spin iron(IV)=O species for a variety of oxygenation reactions. Although synthetic chemists have long sought to mimic this reactivity, the enzyme-like activation of O 2 to form high-spin iron(IV) = O species remains an unrealized goal. Here, we report a metal–organic framework featuring iron(II) sites with a local structure similar to that in α-ketoglutarate-dependent dioxygenases. The framework reacts with O 2 at low temperatures to form high-spin iron(IV) = O species that are characterized using in situ diffuse reflectance infrared Fourier transform, in situ and variable-field Mössbauer, Fe Kβ x-ray emission, and nuclear resonance vibrational spectroscopies. In the presence of O 2 , the framework is competent for catalytic oxygenation of cyclohexane and the stoichiometric conversion of ethane to ethanol.
The extraordinarily rich chemistry of octahedral transition metal halide and chalcohalide cluster... more The extraordinarily rich chemistry of octahedral transition metal halide and chalcohalide clusters has begun to see use in a variety of applications, ranging from catalysis to chemical sensing. In facilitating the design of such cluster-based materials, new synthetic methods for adjusting the core electronic character by atom substitution and for exchanging the six outer terminal ligands are of considerable value. However, the prospect of utilizing a wholly different type of cluster unit arose very recently with the discovery of the molecular species [W6CCl18] n (n = 0–3). Instead of an octahedron, these clusters feature a carbon-centered W6 trigonal prism surrounded by twelve edge-bridging chloride anions and six radially extended terminal chloride ligands. Such units are also known to exist within the one-dimensional compounds A3Nb6SBr17 (A = K, Rb, Cs, and Tl), [4] suggesting that this trigonal-prism structure type may be quite pervasive. Noting that the electronic character of t...
One-step purification and desalination The purification of water for drinking purposes can requir... more One-step purification and desalination The purification of water for drinking purposes can require multiple filtration steps and technologies to remove contaminants such as salts and heavy metals. Some contaminants could have value if recovered, but these are often discharged in the waste streams. Uliana et al. describe a general approach for the fabrication of robust, tunable, adsorptive membranes through the incorporation of porous aromatic framework (PAF) nanoparticles into ion exchange membranes such as those made from sulfonated polymers. Salts are removed using a series of cation and anion exchange membranes, and the PAF particles can be selected to capture specific target ions, such as those of copper, mercury, or iron. This allows for simultaneous desalination and decontamination of the water. Science , this issue p. 296
Advanced materials (Deerfield Beach, Fla.), Jan 8, 2018
Many forward-looking clean-energy technologies hinge on the development of scalable and efficient... more Many forward-looking clean-energy technologies hinge on the development of scalable and efficient membrane-based separations. Ongoing investment in the basic research of microporous materials is beginning to pay dividends in membrane technology maturation. Specifically, improvements in membrane selectivity, permeability, and durability are being leveraged for more efficient carbon capture, desalination, and energy storage, and the market adoption of membranes in those areas appears to be on the horizon. Herein, an overview of the microporous materials chemistry driving advanced membrane development, the clean-energy separations employing them, and the theoretical underpinnings tying membrane performance to membrane structure across multiple length scales is provided. The interplay of pore architecture and chemistry for a given set of analytes emerges as a critical design consideration dictating mass transport outcomes. Opportunities and outstanding challenges in the field are also d...
Angewandte Chemie (International ed. in English), Jan 11, 2017
Hexakis(2,6-diisopropylphenylisocyanide)tantalum is the first isocyanide analogue of the highly u... more Hexakis(2,6-diisopropylphenylisocyanide)tantalum is the first isocyanide analogue of the highly unstable Ta(CO)6 and represents the only well-defined zerovalent tantalum complex to be prepared by conventional laboratory methods. Two prior examples of homoleptic Ta(0) complexes are known, Ta(benzene)2 and Ta(dmpe)3 , dmpe=1,2-bis(dimethylphosphano)ethane, but these have only been accessed via ligand co-condensation with tantalum vapor in a sophisticated metal-atom reactor. Consistent with its 17-electron nature, Ta(CNDipp)6 undergoes facile one-electron oxidation, reduction, or disproportionation reactions. In this sense, it qualitatively resembles V(CO)6 , the only paramagnetic homoleptic metal carbonyl isolable under ambient conditions.
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