Structure and properties of KNi–hexacyanoferrate Prussian Blue Analogues for efficient CO2 capture: Host–guest interaction chemistry and dynamics of CO2 adsorption
Graphical abstract
Introduction
The steady increasing levels of anthropogenic emissions of carbon dioxide (CO2) into the atmosphere are one of the most significant environmental problems for our society. CO2 is the most critical greenhouse gas affecting climate change [[1], [2], [3]] and also represents an essential future carbon feedstock. Thus, the control of CO2 amount is considered a challenging research topic. Many governments are establishing joint efforts [4,5] to encourage the development of new technologies for more efficient CO2 capture.
Current CO2 capture technologies comprise the use of porous solid–state materials that have exceptionally high chemical stability, increased CO2 adsorption capabilities, and fast sorption kinetics to desorb CO2 under mild conditions. In this context, various porous materials with appropriate structural and chemical properties including zeolites [[6], [7], [8]], carbon [[9], [10], [11]], silica–based materials [[12], [13], [14]], and metal organic frameworks (MOFs) [[15], [16], [17], [18], [19], [20], [21], [22], [23], [24]] have been widely investigated for CO2 capture.
Prussian blue (PB) is a simple coordination polymer. The iron metal centers in the PB framework can be replaced by various metal ions to form Prussian blue analogues (PBAs). This opens up large possibilities for adjusting their properties. PBAs represent a large family of materials with a general formula A2xM(3-x)[M’(CN)6]2·nH2O(A = Li, K, Na, Cs, Rb; M = Cr3+, Mn2+,Fe2+/3+, Co2+/3+, Ni2+, Cu2+, Zn2+, and M’= Fe2+/3+, Co2+/3+, Cr3+, Mn2+). In a three–dimensional (3D) face–centered cubic PB network, the metal ions are connected through cyanide bridging ligands to afford a structure with cavities filled with zeolitic water molecules and alkali cations. These materials recently have drawn growing attention due to their superior performance in various applications [25,26], in alkaline ion batteries [27,28], multivalent ion batteries [29], hydrogen storage [27,30,31], optics [32], magnets [33,34], and electrocatalysis [[35], [36], [37], [38]].
In particular, PB and PBAs have shown great potential as efficient adsorbents for CO2 capture [[39], [40], [41]] due to relatively low regeneration energies, efficient physical adsorption profile, and low–cost precursors. However, a very limited number of articles were published on CO2 adsorption and separation application that utilizes PBAs. There exist only several reports [39,40,[42], [43], [44], [45], [46]], which mostly focus on the performance aspect rather than providing a detailed spectroscopic account on the nature of the surface species and elucidation of the particular function of various structural components on the CO2 adsorption mechanism. The high CO2 adsorption capacity of PBAs has mainly been associated with their high surface area and uniform porosity, which provide easy access to the active sites.
Furthermore, PBAs are highly sensitive to small structural distortions induced by external (mechanical) [47,48] or internal (chemical) pressure [[49], [50], [51]]. Thus, the structure of particular PBAs may undergo specific structural rearrangements, which involve alterations in the geometry of the framework through bending of the M′−C≡N−M coordination modes and/or tilting of the [M(CN)6] units around their crystallographic positions. Based on this, many of the unusual and intriguing properties of these materials were explained considering the slight structural distortions. Therefore, many efforts [47,49,[52], [53], [54]] have been devoted to their experimental detection and quantification. A direct evidence of such small structural distortions is, however, a challenging task, especially when the materials exhibit an intrinsic degree of disorder due to the presence of a variable amount of [M(CN)6] entities, alkali cations, and water molecules.
In this work, the effect of nickel and potassium content on the structure and the CO2 adsorption properties of KNi hexacyanoferrate PBAs (K-NiFe-PBAs) was studied by employing samples with different Ni:K atomic ratios of ca. 2.5 and 12, respectively. The samples were synthesized with substantially different porosity and composition containing high– or trace amounts of potassium, as a consequence of charge balance. To study their application as functional materials for efficient CO2 capture, we performed a series of measurements and analysis of the adsorption isotherms, the CO2 storage capacity and the isosteric heat of CO2 adsorption.
The samples were also studied by using a series of complementary characterization experiments including specific surface area, pore volume, pore size distribution, X–ray diffraction (XRD), thermogravimetric and differential thermal (TG–DTA) analysis, Mössbauer spectroscopy, and energy dispersion X–ray spectroscopy in conjunction with scanning electron microscopy (EDX–SEM) to establish a structure & adsorption relationship.
Finally, in situ FTIR spectroscopy was employed to elucidate the host–guest interaction chemistry and dynamics of K-NiFe-PBAs with CO2 and H2O. The study enabled, to the best of our knowledge, is the first FTIR spectroscopic observation of the high sensitivity of the material to structural distortions induced by small changes under water vapor pressure. Moreover, a drastic effect of potassium on the adsorption properties was established.
Section snippets
Synthesis
Two KNi–hexacyanoferrates PBAs with a general formula of KxNiy[Fe(CN)6]2 nH2O were synthesized via a co–precipitation method. K3[Fe(CN)6] and Ni(NO3)2.6H2O precursors used in the synthesis were purchased from Sigma Aldrich and were of analytical grade purity. In the synthetic protocol, 3 mmol of K3[Fe(CN)6] were first dissolved in 50 mL deionized water at room temperature. Then, an aqueous solution of Ni(NO3)2.6H2O (2 or 3 mmol in 50 mL water) were added drop-wise to the above solution. The
Chemical composition and structural analysis via EDX–SEM and XRD
The synthesis method, described in the experimental section, is commonly employed to prepare PBAs [39,56,57] with controlled compositions and morphologies. This can also be confirmed in the current study where the final composition of both prepared materials is almost identical to that pre–set in the synthesis with a Ni:Fe molar ratio, ranging from ∼1:1 to ∼3:2. As a consequence of charge balance, the synthesized K-NiFe-PBAs samples were obtained with a substantially different Ni:K atomic
Conclusions
Two different K‑containing nickel hexacyanoferrate Prussian Blue Analogues (K-NiFe-PBAs) with a cubic crystal structure were synthesized via a co–precipitation method. The composition analysis via EDX–SEM reveals that the as-synthesized compounds are characterized with substantially different Ni:K atomic ratios of ca. 2.5 and 12 and composition containing rich– or trace amounts of potassium due to the charge balance. The FTIR spectroscopy studies reveal the presence of two main coordination
Author statement
Stanislava Andonova: Conceptualization; Investigation; Writing- Original draft preparation; Sina Sadigh Akbari: Sample synthesis; Investigation; Ferdi Karadaş: Investigation; Writing- Reviewing and Editing; Ivanka Spassova: Investigation; Daniela Paneva: Investigation; Konstantin Hadjiivanov: Writing- Reviewing and Editing.
Declaration of Competing Interest
The authors report no declarations of interest.
Acknowledgments
This work was supported by the Bulgarian Ministry of Education and Science (Contract No. DO1-214/28.11.2018) under the National Research Programme “Low-carbon Energy for the Transport and Domestic Use - EPLUS” approved by DCM #577/17.08.2018. S.S.A. thanks TUBITAK for support (Project No: 118Z277).
References (98)
- et al.
Advances in CO2 capture technology-The U.S. Department of Energy’s Carbon Sequestration Program
Int. J. Greenh. Gas Control
(2008) - et al.
Utilization of zeolites as CO2 capturing agents: advances and future perspectives
J. CO2 Util.
(2020) - et al.
Three-dimensional porous carbon frameworks derived from mangosteen peel waste as promising materials for CO2 capture and super capacitors
J. CO2 Util.
(2018) - et al.
One-pot synthesis of highly ordered nitrogen-containing mesoporous carbon with resorcinol–urea–formaldehyde resin for CO2 capture
Carbon
(2014) - et al.
Amine functionalized hierarchical bimodal mesoporous silicas as a promising nanocomposite for highly efficient CO2 capture
J. CO2 Util.
(2019) - et al.
MOFs in carbon capture-past, present and future
J. CO2 Util.
(2020) - et al.
A combined computational and experimental study of high pressure and supercritical CO2 adsorption on Basolite MOFs
Microporous Mesoporous Mater.
(2013) - et al.
CO2 adsorption studies on Prussian blue analogues
Microporous Mesoporous Mater.
(2012) - et al.
The adsorption kinetics of CO2 on copper hexacyanoferrate studied by thermogravimetric analysis
Microporous Mesoporous Mater.
(2018) - et al.
Synthesis, structural elucidation and carbon dioxide adsorption on Zn (II) hexacyanoferrate (II) Prussian blue analogue
Appl. Surf. Sci.
(2016)
Structure and adsorption properties of a porous cooper hexacyanoferrate polymorph
J. Phys. Chem. Solids
Studies on pore systems in catalysts: V. The t method
J. Catal.
Ni–Fe PBA hollow nanocubes as efficient electrode materials for highly sensitive detection of guanine and hydrogen peroxide in human whole saliva
Biosens. Bioelectron.
Microstructural changes induced by thermal treatment of Cobalt(II) hexacyanoferrate(III) compound
J. Solid State Chem.
Enhancement of CO2 adsorption on high surface area activated carbon modified by N2, H2 and ammonia
Chem. Eng. J.
Application of the infrared spectroscopy to the structural study of Prussian blue analogues
Compt. Rend. Chim.
Structure and magnetic properties of copper(II) hexacyanoferrate(III) compound
J. Phys. Chem. Solids
Electrodeposited Prussian blue films: annealing effect
Electrochim. Acta
Facile syntheses of bimetallic Prussian blue analogues (KxM[Fe(CN)6]·nH2O, M=Ni, Co, and Mn) for electrochemical determination of toxic 2-nitrophenol
Electrochim. Acta
Structure–activity relationships of simple molecules adsorbed on CPO-27-Ni metal–organic framework: In situ experiments vs. theory
Catal. Today
Characterization of oxide surfaces and zeolites by carbon monoxide as an IR probe molecule
Adv. Catal.
Ethanol for a sustainable energy future
Science
Global change and the ecology of cities
Science
Recent advances in solid sorbents for CO2 capture and new development trends
Energy Environ. Sci.
Discriminative separation of gases by a “Molecular Trapdoor” mechanism in chabazite zeolites
J. Am. Chem. Soc.
Carbon dioxide and nitrogen adsorption on cation-exchanged SSZ-13 zeolites
Langmuir
Carbon-based adsorbents for post combustion CO2 capture: a critical review
Environ. Sci. Technol.
Emerging trends in porous materials for CO2 capture and conversion
Chem. Soc. Rev.
Fabrication and CO2 adsorption performance of bimodal porous silica hollow spheres with amine-modified surfaces
RSC Adv.
CO2 capture and separations using MOFs: computational and experimental studies
Chem. Rev.
Power of infrared and raman spectroscopies to characterize metal-organic frameworks and investigate their interaction with guest molecules
Chem. Rev.
Adsorption forms of CO2 on MIL-53(Al) and NH2-MIL-53(Al) as revealed by FTIR spectroscopy
J. Phys. Chem. C
Adsorption of CO2 on MIL-53(Al): FTIR evidence of the formation of dimeric CO2 species
Chem. Commun.
An advanced approach for measuring acidity of hydroxyls in confined space: a FTIR study of low-temperature CO and 15N2 adsorption on MOF samples from the MIL-53(Al) series
Phys. Chem. Chem. Phys.
In situ FTIR spectroscopy as a tool for investigation of gas/solid interaction: water-enhanced CO2 adsorption in UiO-66 metal-organic framework
J. Vis. Exp.
Adsorption forms of CO2 on MIL-53(Al) and MIL-53(Al)–OHx as revealed by FTIR spectroscopy
J. Phys. Chem. C
Limitations and high pressure behavior of MOF-5 for CO2 capture
Phys. Chem. Chem. Phys.
Chemical Properties, Structural properties, and energy storage applications of Prussian Blue Analogues
Small
Prussian Blue: a safe pigment with zeolitic-like activity
Int. J. Mol. Sci.
Formation of Prussian‐Blue‐Analog nanocages via a direct etching method and their conversion into Ni–Co‐mixed oxide for enhanced oxygen evolution
Adv. Mater.
High-quality Prussian blue crystals as superior cathode materials for room-temperature sodium-ion batteries
Energy Environ. Sci.
Copper hexacyanoferrate nanoparticles as cathode material for aqueous Al-ion batteries
J. Mater. Chem. A
Hydrogen storage in the dehydrated Prussian Blue Analogues M3[Co(CN)6]2 (M = Mn, Fe, Co, Ni, Cu, Zn)
J. Am. Chem. Soc.
Hydrogen storage in Prussian Blue Analogues: H2 interaction with the metal found at the cavity surface
Energy Fuels
Large optical third-order nonlinearities in a switchable Prussian blue analogue
Optical Mater. Express
Novel magnetic functionalities of Prussian blue analogs
Dalton Trans.
Magnetism and photomagnetism of Prussian Blue Analogue nanoparticles embedded in porous metal oxide ordered nanostructures
Eur. J. Inorg. Chem.
Precious‐metal‐free dye‐sensitized photoanode for water oxidation: a nanosecond‐long excited‐state lifetime through a Prussian Blue Analogue
Angew. Chem. Int. Ed.
Cited by (9)
Constructing N-doped carbon beads-encapsulated CoMn<inf>2</inf>O<inf>4</inf> microboxes with pyramidal walls for enhanced Li storage
2022, Materials Today EnergyCitation Excerpt :The XRD pattern (Fig. S1a) shows its good crystallinity. The three peaks in the FTIR spectrum (Fig. S1b) at 3415, 2164 and 1612 cm−1 are assigned to the O–H stretching, the C≡N stretching of Co–Mn PBA, and the C=O stretching of the PVP amide unit due to the residual PVP in the sample [26]. Furthermore, the EDS result (Fig. S1c) indicates that the atomic ratio of Co and Mn is around 1:2, and the atomic ratio of C and N is close to 1:1 in Co–Mn PBA.
Microporous prussian blue analogs and their application for environmental remediation: A deeper look from the structure-property-functionality perspective
2022, Microporous and Mesoporous MaterialsCitation Excerpt :This result is consistent with a significant number of vacancies when the K is present at trace levels, with a lower occupation in the structure, thus creating larger cavities and more accessible channels for gas adsorption. The superior CO2 adsorption can be explained by the structural differences between the two Ni–K-PBA given by the amount of introduced K ions inside the material [140]. The results obtained demonstrate the potential catalytic application of PBA for ozone decomposition into oxygen, which represents an appealing strategy for air decontamination systems.
Role of heat dissipation on carbon dioxide capture performance in biomethane upgrading system using pressure swing adsorption
2022, Separation and Purification TechnologyCitation Excerpt :Selective adsorption of CO2 based on surface chemistry interaction is another possible technique to improve the selectivity [19]. Surface chemistry interaction such as H-bonding, polarity, quadruple moment, and the surface properties of the adsorbent can also be exploited to improve the selectivity [20]. For example, quadrupole moment of CO2 in a CO2/CH4 system and the non-polarity of the CH4 molecule can be exploited to improve the selectivity further [21,22].
Evaluation of thermal effects on carbon dioxide breakthrough curve for biogas upgrading using pressure swing adsorption
2021, Energy Conversion and ManagementCitation Excerpt :Selective adsorption of CO2 based on surface chemistry interaction is another possible technique to boost selectivity [16]. Surface chemistry interaction is following the adsorbate features such as H-bonding, polarity, quadruple moment, and the surface properties of the adsorbent [52]. For CO2/CH4 system, the adsorption occurs based on the large quadrupole moment of CO2 whereas the CH4 molecule is nonpolar [53 54].