Wet flue gas CO<sub>2</sub> capture and utilization using one-dimensional metal–organic chains

Chiu, Nan‐Chieh; Loughran, Ryan; Gładysiak, Andrzej; Vismara, Rebecca; Park, Ah‐Hyung Alissa; Stylianou, Kyriakos C.

doi:10.1039/d2nr04156a

Cited by 15 publications

(12 citation statements)

References 39 publications

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“…Heterocyclic C-H bonds originating from pzdc 3and the imidazolate part of ade point into these voids. As described in our previous report, [5] activation of [Ni3(pzdc)2(ade)2(H2O)4]•2.18H2O leads to the complete removal of H2O molecules coordinated to Ni 2+ as well as those non-covalently occluded in the pores, leaving Ni 2+ cations coordinatively unsaturated. [5,21] The crystal structure suggests the presence of two symmetrically inequivalent open metal sites, NiA and NiB (Figure 1a) in the activated material, and their coordination geometries are thought to change from octahedral to square pyramidal (for NiA), and from octahedral to square planar (for NiB).…”

Section: Resultssupporting

confidence: 58%

“…Consequently, the material changes its color from sky-blue to lavender. [5,21] The permanent porosity of [Ni3(pzdc)2(ade)2] was confirmed with N2 isotherms collected at 77 K and 1 bar (Figures S3). Activated [Ni3(pzdc)2(ade)2] displayed a Brunauer-Emmett-Teller (BET) surface area of 160 m 2 /g, a pore volume of 0.0769 cm 3 /g, and a pore size distribution centered at 0.67 nm (Figure S4).…”

Section: Resultsmentioning

confidence: 54%

“…[3] Understanding interactions between the host material and guest molecules are vital to rationally assessing the viability of porous materials for a given desired application. [4] The crystallinity of porous materials, namely zeolites and MOFs, has enabled the study of intermolecular interactions of these materials with guest molecules on the atomic scale; this has resulted in the rational design and synthesis of new materials with improved performance for carbon capture, [5] hydrocarbon separation, [6] storage of methane and hydrogen (H2), [7] and detection of gases such as ammonia and hydrogen sulfide. [8] The harmful environmental effects of excessive combustion of fossil fuels, together with the intermittence of current sources of renewable energy, incentivize the search for alternative energy solutions.…”

Section: Introductionmentioning

confidence: 99%

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Hydrogen Adsorption in Ultramicroporous Metal-organic Frameworks Possessing Silent Open Metal Sites

Chiu

Compton

Gładysiak

et al. 2023

Preprint

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Herein, we report the use of an ultramicroporous (pore size <0.7 nm) metal-organic framework (MOF), [Ni3(pzdc)2(ade)2(H2O)4]2.18H2O (H3pzdc: pyrazole-3,5-dicarboxylic acid, ade: adenine), for hydrogen (H2) adsorption. Upon activation, [Ni3(pzdc)2(ade)2] was generated, and in situ carbon monoxide loading transmission infrared spectroscopy revealed that open Ni(II) sites could be generated. The MOF displayed a Brunauer-Emmett-Teller (BET) surface area of 160 m2/g. Hydrogen adsorption collected on this MOF at 77 K revealed a steep uptake at low pressure, and H2 uptake saturation was achieved at 0.15 bar. The affinity of this MOF for H2 is 9.7 1.0 kJ/mol. An interplay of in situ H2 loading experiments and computations confirmed that H2 does not bind to the open Ni(II) sites of the MOF, and the observed high affinity of the MOF for H2 is mainly attributed to its narrow pore size. To shed light on the impact of ultramicropores on H2 uptake, we experimentally compared the H2 uptake per surface area unit as a function of the pore size of other ultramicroporous, microporous, and mesoporous MOFs. Our results showcase that ultramicropores contribute the most to H2 uptake, and the size, shape, and functionality of our MOF are ideal and can be used as guiding principles for the design and synthesis of novel adsorbents for efficient H2 storage and delivery.

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Section: Resultssupporting

confidence: 58%

Section: Resultsmentioning

confidence: 54%

Section: Introductionmentioning

confidence: 99%

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Hydrogen Adsorption in Ultramicroporous Metal-organic Frameworks Possessing Silent Open Metal Sites

Chiu

Compton

Gładysiak

et al. 2023

Preprint

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“…Moreover, it is important to highlight that CO 2 and H 2 O strongly interact with each other, and the presence of H 2 O can hydrolyze the metal–organic coordination bonds in MOFs, resulting in the degradation of the MOFs’ crystalline structure. − For instance, Mg-MOF-74 possesses open Mg(II) sites, and when exposed to 70% RH, the CO 2 uptake of Mg-MOF-74 decreased by 84%, accompanied by a significant reduction in the surface area. − The demanding conditions encountered in practical applications present new challenges for the stable operation of polymer-MOF MMMs. Here, we used Pebax 2533 (poly(ether- block -amide)) as the matrix, incorporated novel hydroxamate-based MOFs as the filler to prepare MMMs, and conducted groundbreaking research on the CO 2 separation performance of MMMs under a series of humidity conditions, proposing the separation mechanism of large-pore MOFs under the coexistence of CO 2 , N 2 , and H 2 O.…”

Section: Introductionmentioning

confidence: 99%

Impact of Humidity on the CO₂/N₂ Separation Performance of Pebax-MOF Mixed Matrix Membranes

Qin,

Feng,

Yin

et al. 2023

Ind. Eng. Chem. Res.

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Postcombustion capture has been an important field for CO2 capture, but its high H2O content has been a significant barrier to the performance of mixed matrix membranes (MMMs). In this study, a series of humidity values were established, and two types of MOFs (SUM-1 and SUM-9) were used in Pebax 2533 (poly(ether-block-amide)) to prepare MMMs to explore CO2/N2 separation performance. At 35 °C and 2 bar, the CO2 permeability of Pebax-SUM-1 was 380.9, 433.1, 405.4, and 401.7 Barrer, respectively, when the relative humidity (RH) changed from 0, 30, 60, to 100%, and the CO2/N2 selectivity was 20.5, 19.0, 18.1, and 17.0, respectively. The CO2 permeability of Pebax-SUM-9 was 390.9, 387.4, 412.5, and 452.4 Barrer, with the CO2/N2 selectivities being 18.5, 19.9, 20.0, and 19.7, respectively. The CO2/N2 selectivity had no significant fluctuations. A hypothesis has been proposed that the large-pore MOFs could only provide transport channels and could not screen CO2, and the CO2/N2 selectivity would mainly be provided by the polymer matrix. Under high humidity conditions, the CO2 transport channels with large-pore MOFs might fail due to competition between H2O and CO2. This study investigated the influence of a series of RH on MMMs separation performance. The proposed theory suggests that there might be an optimal humidity range for the CO2 permeability of MMMs in humid conditions, which can be useful to guide the design of porous fillers for future MMMs development.

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“…3,4 Understanding the interactions between the host material and guest molecules is vital to rationally assess the viability of porous materials for a desired application. 5 The crystallinity of porous materials, namely zeolites and MOFs, has enabled the study of intermolecular interactions of these materials with guest molecules on the atomic scale; this has resulted in the rational design and synthesis of new materials with improved performance for carbon capture, 6 hydrocarbon separation, 7 storage of methane and hydrogen (H 2 ), 8,9 and detection of gases such as ammonia and hydrogen sulfide. 10−12 The harmful environmental effects of excessive combustion of fossil fuels, together with the intermittent current sources of renewable energy, incentivize the search for alternative energy solutions.…”

Section: ■ Introductionmentioning

confidence: 99%

Hydrogen Adsorption in Ultramicroporous Metal–Organic Frameworks Featuring Silent Open Metal Sites

Chiu,

Compton,

Gładysiak

et al. 2023

ACS Appl. Mater. Interfaces

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In this study, we utilized an ultramicroporous metal− organic framework (MOF) named [Ni 3 (pzdc) 2 (ade) 2 (H 2 O) 4 ]• 2.18H 2 O (where H 3 pzdc represents pyrazole-3,5-dicarboxylic acid and ade represents adenine) for hydrogen (H 2 ) adsorption. Upon activation, [Ni 3 (pzdc) 2 (ade) 2 ] was obtained, and in situ carbon monoxide loading by transmission infrared spectroscopy revealed the generation of open Ni(II) sites. The MOF displayed a Brunauer− Emmett−Teller (BET) surface area of 160 m 2 /g and a pore size of 0.67 nm. Hydrogen adsorption measurements conducted on this MOF at 77 K showed a steep increase in uptake (up to 1.93 mmol/g at 0.04 bar) at low pressure, reaching a H 2 uptake saturation at 2.11 mmol/g at ∼0.15 bar. The affinity of this MOF for H 2 was determined to be 9.7 ± 1.0 kJ/mol. In situ H 2 loading experiments supported by molecular simulations confirmed that H 2 does not bind to the open Ni(II) sites of [Ni 3 (pzdc) 2 (ade) 2 ], and the high affinity of the MOF for H 2 is attributed to the interplay of pore size, shape, and functionality.

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Wet flue gas CO₂ capture and utilization using one-dimensional metal–organic chains

Abstract: Herein we describe the use of a metal-organic framework (MOF) with a composition of [Ni3(pzdc)2(ade)2(H2O)1.5](H2O)1.3, for the selective capture of carbon dioxide (CO2) from wet flue gas followed by its...

Cited by 15 publications

References 39 publications

Hydrogen Adsorption in Ultramicroporous Metal-organic Frameworks Possessing Silent Open Metal Sites

Hydrogen Adsorption in Ultramicroporous Metal-organic Frameworks Possessing Silent Open Metal Sites

Impact of Humidity on the CO₂/N₂ Separation Performance of Pebax-MOF Mixed Matrix Membranes

Hydrogen Adsorption in Ultramicroporous Metal–Organic Frameworks Featuring Silent Open Metal Sites

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Wet flue gas CO2 capture and utilization using one-dimensional metal–organic chains

Abstract: Herein we describe the use of a metal-organic framework (MOF) with a composition of [Ni3(pzdc)2(ade)2(H2O)1.5](H2O)1.3, for the selective capture of carbon dioxide (CO2) from wet flue gas followed by its...

Cited by 15 publications

References 39 publications

Hydrogen Adsorption in Ultramicroporous Metal-organic Frameworks Possessing Silent Open Metal Sites

Hydrogen Adsorption in Ultramicroporous Metal-organic Frameworks Possessing Silent Open Metal Sites

Impact of Humidity on the CO2/N2 Separation Performance of Pebax-MOF Mixed Matrix Membranes

Hydrogen Adsorption in Ultramicroporous Metal–Organic Frameworks Featuring Silent Open Metal Sites

Contact Info

Product

Resources

About

Wet flue gas CO₂ capture and utilization using one-dimensional metal–organic chains

Impact of Humidity on the CO₂/N₂ Separation Performance of Pebax-MOF Mixed Matrix Membranes