Thermal decarboxylation for the generation of hierarchical porosity in isostructural metal–organic frameworks containing open metal sites

Drake, Hannah F.; Xiao, Zhifeng; Day, Gregory S.; Vali, Shaik Waseem; Chen, Wenmiao; Wang, Qi; Huang, Yutao; Yan, Tian‐Hao; Kuszynski, Jason E.; Lindahl, Paul A.; Ryder, Matthew R.; Zhou, Hong‐Cai

doi:10.1039/d1ma00163a

Cited by 16 publications

(17 citation statements)

References 38 publications

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“…This is indicative of the noticeably stronger Fe–C binding strengths. Metal identity and oxidation state have been known to influence other properties of PCN-250 as well. , Additionally, there was a slight increase in the observed acetylene carbon–carbon bond length. The bond length of acetylene (1.1974 Å as a free molecule) was observed to increase from 1.2007 in the Fe(III) system all the way to 1.2018 in the nickel-bound Fe 2 Ni system.…”

Section: Resultsmentioning

confidence: 98%

“…For comparison, two alternative samples were utilized to determine the performance of reducibility, open metal site formation, and backdonation: PCN-250-Al, which has not been observed to undergo a reductive decarboxylation mechanism, 30 and PCN-250-Fe 2 Ni, which is already in a mixed valent Fe(III)/Ni(II) state, 30 were also subjected to a 250 °C activation and acetylene adsorption experiments (Tables S6 and S7 and Figures S23−S25). The nonreducible Al centers result in lower gas uptake performance compared to the standard Fe 3 variant (Figure S23) while also resulting in a heat of adsorption after 250 °C activation that is nearly identical to that of the 150 °C-activated PCN-250-Fe (Figure S26a).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Two of the most well-known MOFs with the Fe 3 O cluster are MIL-100 and PCN-250 (also known as MIL-127) . Due to the redox accessibility of iron, the Fe 3 O cluster has been noted to undergo reduction events in both MOFs, ,− producing a mixed valent μ 3 -oxo Fe(III) 2 Fe(II) cluster under a high-temperature (∼220 °C) thermal treatment. This mixed valent state is particularly important for the adsorption of certain unsaturated molecules, such as alkenes and alkynes, as the Fe(II) sites have improved π-backdonation capabilities compared to the Fe(III) centers. , This improved backdonation allows for a higher adsorption enthalpy at these open metal sites, thus leading to an improvement in adsorption capacity, particularly at the low adsorption pressures …”

Section: Introductionmentioning

confidence: 99%

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Evaluation of Iron-Based Metal–Organic Framework Activation Temperatures in Acetylene Adsorption

Day¹,

Rowe

Ybanez³

et al. 2022

Inorg. Chem.

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One of the major issues regarding long-term human space exploration is the need for a breathable atmosphere. A major component toward achieving this goal is both the removal of exhaled carbon dioxide (CO2) and the generation or recovery of oxygen (O2). NASA’s current technology only operates at about 50% efficiency due to the need to vent the methane that is produced during the CO2 reduction process. One method of improving the efficiency of this process is through plasma pyrolysis, wherein the methane is pyrolyzed to produce hydrogen and various dehydrogenated carbon byproducts. In this process, acetylene is one of the main components of this byproduct stream. Unfortunately, while the concentration of this effluent is generally high in hydrogen (>90% typically), the presence of the acetylene waste product can act as a poison for the ruthenium–alumina catalyst used in the CO2-reducing Sabatier process, requiring a removal step. Metal–organic frameworks (MOFs) represent a valuable method for removing these unsaturated hydrocarbons due to their high tunability, particularly through the incorporation of open metal sites. In this study, two common iron-based MOFs, MIL-100 and PCN-250, were studied for their ability to adsorb acetylene. A combination of gas adsorption analysis and density functional theory calculation results shows the ability of these materials to undergo a thermal-induced reduction event, which results in an improvement in gas adsorption performance. This improvement in gas performance appears to be at least partially due to the increased presence of π-backbonding toward the acetylene molecules.

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Section: Resultsmentioning

confidence: 98%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Evaluation of Iron-Based Metal–Organic Framework Activation Temperatures in Acetylene Adsorption

Day¹,

Rowe

Ybanez³

et al. 2022

Inorg. Chem.

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“…The powder patterns, N 2 isotherms, and porosity measurements matched well with previous reports (shown in the Supporting Information). 43−46 In the analogues of PCN-250-M, where M = Al, In, or Sc (also called Al-soc-MOF-1d, In-soc-MOF-1a, and Sc-ABTC/socMOF), 43,45,47,48 the structures do not undergo thermal generation of open metal sites. 43 However, we previously reported that PCN-250-Fe could undergo thermal decarboxylation under standard activation conditions, resulting in open metal sites.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…43−46 In the analogues of PCN-250-M, where M = Al, In, or Sc (also called Al-soc-MOF-1d, In-soc-MOF-1a, and Sc-ABTC/socMOF), 43,45,47,48 the structures do not undergo thermal generation of open metal sites. 43 However, we previously reported that PCN-250-Fe could undergo thermal decarboxylation under standard activation conditions, resulting in open metal sites. 49 Therefore, to avoid the influence of open metal site formation and to provide an accurate comparison between the isomorphs, the Fe-based material was also activated under supercritical CO 2 .…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Influence of Metal Identity on Light-Induced Switchable Adsorption in Azobenzene-Based Metal–Organic Frameworks

Drake

Xiao

Day

et al. 2022

ACS Appl. Mater. Interfaces

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Energy-efficient capture and release of small gas molecules, particularly carbon dioxide (CO2) and methane (CH4), are of significant interest in academia and industry. Porous materials such as metal–organic frameworks (MOFs) have been extensively studied, as their ultrahigh porosities and tunability enable significant amounts of gas to be adsorbed while also allowing specific applications to be targeted. However, because of the microporous nature of MOFs, the gas adsorption performance is dominated by high uptake capacity at low pressures, limiting their application. Hence, methods involving stimuli-responsive materials, particularly light-induced switchable adsorption (LISA), offer a unique alternative to thermal methods. Here, we report the mechanism of a well-known LISA system, the azobenzene-based material PCN-250, for CO2 and CH4 adsorption. There is a noticeable difference in the LISA effect dependent on the metal cluster involved, with the most significant being PCN-250-Al, where the adsorption can change by 83.1% CH4 and 56.1% CO2 at 298 K and 1 bar and inducing volumetric storage changes of 36.2 and 33.9 cm3/cm3 at 298 K between 5 and 85 bar (CH4) and 2 and 9 bar (CO2), respectively. Using UV light in both single-crystal X-ray diffraction and gas adsorption testing, we show that upon photoirradiation, the framework undergoes a “localized heating” phenomenon comparable to an increase of 130 K for PCN-250-Fe and improves the working capacity. This process functions because of the constrained nature of the ligand, preventing the typical trans-to-cis isomerization observed in free azobenzene. In addition, we observed that the degree of localized heating is highly dependent on the metal cluster involved, with the series of isostructural PCN-250 systems showing variable performance based upon the degree of interaction between the ligand and the metal center.

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Oxidative decarboxylation of arylacetic acids and arylacetic esters with singlet molecular oxygen generated from trans-5-hydroperoxy-3,5-dimethyl-1,2-dioxolan-3-yl ethaneperoxate

Najminejad

2024

J Chem Sci

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Thermal decarboxylation for the generation of hierarchical porosity in isostructural metal–organic frameworks containing open metal sites

Abstract: The effect of metal-cluster redox identity on the thermal decarboxylation of a series of isostructural metal-organic frameworks (MOFs) with tetracarboxylate-based ligands and trinuclear μ3-oxo clusters was investigated. The PCN-250 series...

Cited by 16 publications

References 38 publications

Evaluation of Iron-Based Metal–Organic Framework Activation Temperatures in Acetylene Adsorption

Evaluation of Iron-Based Metal–Organic Framework Activation Temperatures in Acetylene Adsorption

Influence of Metal Identity on Light-Induced Switchable Adsorption in Azobenzene-Based Metal–Organic Frameworks

Oxidative decarboxylation of arylacetic acids and arylacetic esters with singlet molecular oxygen generated from trans-5-hydroperoxy-3,5-dimethyl-1,2-dioxolan-3-yl ethaneperoxate

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