Water Adsorption Properties of Fe(pz)[Pt(CN)<sub>4</sub>] and the Capture of CO<sub>2</sub> and CO

Alvarado-Alvarado, Daniel; González‐Estefan, Juan H.; Flores, Jose; Álvarez, J. Raziel; Aguilar-Pliego, Julia; Islas‐Jácome, Alejandro; Chastanet, Guillaume; González‐Zamora, Eduardo; Lara-García, Hugo A.; Alcántar-Vázquez, Brenda; Gonidec, Mathieu; Ibarra, Ilich A.

doi:10.1021/acs.organomet.9b00711

Cited by 18 publications

(20 citation statements)

References 52 publications

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“…In order to examine the crystalline structure of the prepared samples, we carried out X-ray diffraction (XRD) measurements ( Figure 2 a). The XRD pattern of the reference sample is nearly identical to XRD to that presented by Alvarado et al [ 22 ]. The positions of the reflections indicate tetragonal crystalline structure with the following unit cell parameters: a = b = 7.45 Å, c = 7.26 Å, which are congruent with the results for the high spin state of non-dehydrated nanocrystals [ 23 ].…”

Section: Resultssupporting

confidence: 74%

Thin Films of Nanocrystalline Fe(pz)[Pt(CN)4] Deposited by Resonant Matrix-Assisted Pulsed Laser Evaporation

et al. 2021

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Prior studies of the thin film deposition of the metal-organic compound of Fe(pz)Pt[CN]4 (pz = pyrazine) using the matrix-assisted pulsed laser evaporation (MAPLE) method, provided evidence for laser-induced decomposition of the molecular structure resulting in a significant downshift of the spin transition temperature. In this work we report new results obtained with a tunable pulsed laser, adjusted to water resonance absorption band with a maximum at 3080 nm, instead of 1064 nm laser, to overcome limitations related to laser–target interactions. Using this approach, we obtain uniform and functional thin films of Fe(pz)Pt[CN]4 nanoparticles with an average thickness of 135 nm on Si and/or glass substrates. X-ray diffraction measurements show the crystalline structure of the film identical to that of the reference material. The temperature-dependent Raman spectroscopy indicates the spin transition in the temperature range of 275 to 290 K with 15 ± 3 K hysteresis. This result is confirmed by UV-Vis spectroscopy revealing an absorption band shift from 492 to 550 nm related to metal-to-ligand-charge-transfer (MLCT) for high and low spin states, respectively. Spin crossover is also observed with X-ray absorption spectroscopy, but due to soft X-ray-induced excited spin state trapping (SOXIESST) the transition is not complete and shifted towards lower temperatures.

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Section: Resultssupporting

confidence: 74%

Thin Films of Nanocrystalline Fe(pz)[Pt(CN)4] Deposited by Resonant Matrix-Assisted Pulsed Laser Evaporation

et al. 2021

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“…For CO2, the saturation loading is about 1.5 mol of CO2 per Fe mol, as determined experimentally from adsorption isotherms. 21,24 In the absence, to the best of our knowledge, of published absorption isotherms for CO, we estimate the saturation loading at about 2 CO mol / Fe mol from the kinetic uptake experiments reported by Ibarra et al 27 Our ND, DFT and INS results are consistent with these saturation loading values (vide infra).…”

Section: Neutron Diffractionsupporting

confidence: 71%

“…Recently, the member of the series Fe(pz)[M(CN)4] with M = Pt(II) has shown a significant higher CO2 and CO uptake capacities compared to other MOFs with larger surface areas. 27 In this work, we focus our interest in these Hofmann-like clathrates upon CO2 and CO loading. We report a detailed study of gas adsorption mechanism of CO and CO2 in Fe(pz)[Pt(CN)4] in the low-spin state by means of neutron scattering techniques and density-functional theory calculations.…”

Section: Introductionmentioning

confidence: 99%

CO and CO2 Adsorption Mechanism in Fe(pz)[Pt(CN)4] Probed by Neutron Scattering and Density-Functional Theory Calculations

Fernández-Blanco

Piñeiro‐López

Jiménez‐Ruiz

et al. 2022

Preprint

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We study the binding mechanism of CO and CO2 in the porous spin-crossover compound Fe(pz)[Pt(CN)4] by combining neutron diffraction (ND), inelastic neutron scattering (INS) and density-functional theory (DFT) calculations. Two adsorption sites are identified, above the open-metal site and between the pyrazine rings. For CO adsorption, the guest molecules are parallel to the neighboring gas molecules and perpendicular to the pyrazine planes. For CO2, the molecules adsorbed on-top of the open-metal site are perpendicular to the pyrazine rings and those between the pyrazines are almost parallel to them. These configurations are consistent with the INS data which are in good agreement with the computed generalized phonon density of states. The most relevant signatures of the binding occur in the spectral region around 100 cm−1 and 400 cm−1. The first peak blue-shifts for both CO and CO2 adsorption, while the second red-shifts for CO and remains nearly unchanged for CO2. These spectral changes depend both from steric effects and the nature of the interaction. The interprtation of the INS data as supported by the computed binding energy and the molecular orbital analysis are consistent with a physisorption mechanism for both gases. This work shows the strength of the combination of neutron techniques and DFT calculations to characterize in detail the gas adsorption mechanism in this type of materials.

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“…Thermogravimetric Analysis When using TGA alone, the sample is often prehumidified at a desired temperature in the presence of an inert gas with a constant relative humidity, then exposed to the CO 2 -containing feed with the same RH, at the same temperature, while monitoring the weight gain (Figure 1a). 76,139,162,[191][192][193][194][196][197][198]201,202,206 Alternatively, both measurements can been undertaken separately (Figure 1b). 196 Assuming that the adsorption of water at a given RH is not affected by CO 2 , and the adsorption of the inert gas, often N 2 , is negligible, the sample weights at both equilibria would yield the corresponding water and CO 2 uptakes.…”

Section: Measuring Co 2 Uptake Under Humid Conditionsmentioning

confidence: 99%

Understanding the Effect of Water on CO₂ Adsorption

2021

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Carbon capture from large sources and ambient air is one of the most promising strategies to curb the deleterious effect of greenhouse gases. Among different technologies, CO2 adsorption has drawn widespread attention mostly because of its low energy requirements. Considering that water vapor is a ubiquitous component in air and almost all CO2-rich industrial gas streams, understanding its impact on CO2 adsorption is of critical importance. Owing to the large diversity of adsorbents, water plays many different roles from a severe inhibitor of CO2 adsorption to an excellent promoter. Water may also increase the rate of CO2 capture or have the opposite effect. In the presence of amine-containing adsorbents, water is even necessary for their long-term stability. The current contribution is a comprehensive review of the effects of water whether in the gas feed or as adsorbent moisture on CO2 adsorption. For convenience, we discuss the effect of water vapor on CO2 adsorption over four broadly defined groups of materials separately, namely (i) physical adsorbents, including carbons, zeolites and MOFs, (ii) amine-functionalized adsorbents, and (iii) reactive adsorbents, including metal carbonates and oxides. For each category, the effects of humidity level on CO2 uptake, selectivity, and adsorption kinetics under different operational conditions are discussed. Whenever possible, findings from different sources are compared, paying particular attention to both similarities and inconsistencies. For completeness, the effect of water on membrane CO2 separation is also discussed, albeit briefly.

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Water Adsorption Properties of Fe(pz)[Pt(CN)₄] and the Capture of CO₂ and CO

Cited by 18 publications

References 52 publications

Thin Films of Nanocrystalline Fe(pz)[Pt(CN)4] Deposited by Resonant Matrix-Assisted Pulsed Laser Evaporation

Thin Films of Nanocrystalline Fe(pz)[Pt(CN)4] Deposited by Resonant Matrix-Assisted Pulsed Laser Evaporation

CO and CO2 Adsorption Mechanism in Fe(pz)[Pt(CN)4] Probed by Neutron Scattering and Density-Functional Theory Calculations

Understanding the Effect of Water on CO₂ Adsorption

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Water Adsorption Properties of Fe(pz)[Pt(CN)4] and the Capture of CO2 and CO

Cited by 18 publications

References 52 publications

Thin Films of Nanocrystalline Fe(pz)[Pt(CN)4] Deposited by Resonant Matrix-Assisted Pulsed Laser Evaporation

Thin Films of Nanocrystalline Fe(pz)[Pt(CN)4] Deposited by Resonant Matrix-Assisted Pulsed Laser Evaporation

CO and CO2 Adsorption Mechanism in Fe(pz)[Pt(CN)4] Probed by Neutron Scattering and Density-Functional Theory Calculations

Understanding the Effect of Water on CO2 Adsorption

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Water Adsorption Properties of Fe(pz)[Pt(CN)₄] and the Capture of CO₂ and CO

Understanding the Effect of Water on CO₂ Adsorption