Synthesis strategies of metal-organic frameworks for CO2 capture
Abstract
The high consumption of fossil energy has led to increasing concentrations of carbon dioxide (CO2) in the atmosphere, making carbon capture and separation a research hotspot in this century. As novel porous materials, metal-organic frameworks (MOFs) are widely used for CO2 capture due to their unique structures and tunable properties. Currently, several relatively mature strategies have been applied to synthesize MOFs for CO2 capture. Herein, we investigate strategies for tuning the pore windows, pore sizes, open metal sites, and post-synthesis or pre-synthesis modifications of MOFs from the perspective of CO2 capture performance. Furthermore, we summarize the relevant CO2 capture technologies and research advances and describe the application of different strategies in the synthesis of CO2 capture-oriented MOFs.
Keywords
INTRODUCTION
Since the Industrial Revolution, the extraction and consumption of fossil fuels have caused a remarkable expansion of greenhouse gases in the atmosphere. The Earth's climate is undergoing major changes characterized by global warming, according to numerous authoritative studies[1-4]. Compared to other greenhouse gases, carbon dioxide (CO2) has a weaker greenhouse effect, but it has the highest proportion in the atmosphere, with its warming effect accounting for about 60% of the total warming effect among all greenhouse gases[5,6]. Therefore, it is urgent to work out an environment-friendly CO2 capture technology to alleviate the greenhouse effect[7,8].
In recent years, the development of carbon capture and separation (CCS) technology has attracted social attention. Adsorbents that can be used for CO2 capture include activated carbon, zeolite, alumina, metal oxides (CaO, MgO, K2O, Li2O), metal-organic frameworks (MOFs), and other surface-modified porous media[9-12]. Compared to traditional inorganic porous materials, MOFs have many advantages and show great application potential in CO2 adsorption and sequestration. One is the modifiability of its secondary building units (SBUs) and organic ligands. Through the modification of inorganic/organic nodes on functionality groups, the fine-tuning of the pore size and channel environment in MOFs can be precisely achieved, and then MOFs oriented to CO2 capture can be synthesized[13-15]. On the other hand, due to their high density of active sites, high stability, and rich topological structures, MOFs have distinct advantages, such as mild reaction conditions and easy adsorption and sequestration of CO2[16-18].
A large number of relevant papers and reviews have been published[19,20]. In contrast to the published reviews, this paper presents the current CO2 capture technology and related adsorbents. Then, the parameters for evaluating the performance of CO2 capture adsorbents are presented to achieve the best capture capacity and reduce costs and energy expenditure. In addition, recent advances in MOF-based CO2 capture methods and ways to improve the capture performance of the materials are explored. The strategies and methods described in this review will not only provide new propositions for the construction of
CO2 CAPTURE
In September 2020, the “Address at the General Debate of the 75th Session of the United Nations General Assembly” and the “Address at the United Nations Biodiversity Summit” proposed that China should aim to achieve CO2 peak emissions by 2030 and carbon neutrality by 2060. In addition, many countries around the world have enacted policies or legislation to advance the goal of carbon neutrality. So far, 29 countries and regions have pledged to be carbon neutral[21]. The prevailing view is that CCS may be the cheapest technology to reduce emissions in the long term and will gain time to develop new technologies such as alternative energy sources[22,23].
CO2 capture technology
CCS technology refers to the separation of CO2 from industrial and energy-related production activities and its long-term sequestration in natural underground reservoirs in order to reduce CO2 emissions to the atmosphere[24,25]. There are three main components to CCS technology: (1) CO2 capture from fixed carbon sources (e.g., power plants); (2) CO2 compression and transport; and (3) CO2 storage.
In terms of the capture process, there are three main types of CO2 capture technologies: pre-combustion capture, post-combustion capture, and oxy-fuel combustion[26] [Figure 1]. Pre-combustion capture uses new gasification technology to convert fossil fuels into H2 and CO2, which are then captured before combustion. Compared with direct coal combustion, this technology has higher fossil fuel utilization, less waste disposal, and less water consumption. In addition, due to high CO2/H2 gas pressure and CO2 concentration, the energy consumption of pre-combustion CO2 capture is only 10%-16% of the total energy consumption, which is about half of the energy consumption of post-combustion capture. However, the high energy consumption of the fuel conversion step limits its further development[27-29]. Oxy-fuel combustion is based on burning fossil fuels in oxygen-rich gases to obtain high concentrations of CO2, which is direct sequestration and utilization. Due to the removal of N2 in the air, the volume of combustion gas is reduced, so the volume of flue gas produced after combustion is reduced to 1/5-1/3 of that of conventional coal-fired boilers. Meanwhile, the concentration of CO2 in the flue gas is high, making the cost of capturing CO2 lower. However, this technology is not ideal for CO2 capture due to its high energy consumption and investment costs[30,31]. Post-combustion capture means capturing CO2 in the flue gas from the combustion emissions. Since the partial pressure of CO2 after capture is low, it is necessary to pressurize the CO2 before storage, which increases the operating cost. Even so, post-combustion capture has the following advantages over other capture techniques: (1) A wide range of applications. Post-combustion capture technology can not only separate CO2 from flue gas but also capture NOX and SOX to achieve the purpose of denitrification and desulfurization; (2) Strong applicability. The trapping device is installed in the flue gas tail of the power plant, which has no influence on the existing power generation equipment and; (3) Relatively mature development and flexible operation[32-34]. Therefore, post-combustion capture is a common CO2 capture technology.
Figure 1. Three basic routes (post-combustion capture, pre-combustion capture, and oxy-fuel combustion) of CO2 capture in industry.
In addition, CO2 capture technology can be classified based on different capture methods, including chemical absorption[35], membrane separation[36-38], biological immobilization[39], adsorption[40-43], and other approaches. Among them, the adsorption method is the most competitive CO2 capture technique.
CO2 capture adsorbent
Adsorption is the uptake of molecules or ions from the surrounding liquid or gas by the surface of a solid substance. The adsorption method has been widely studied by scholars for its advantages of low cost and simple operation[44]. However, its practical application requires the design and synthesis of an easily regenerated and durable adsorbent material. Generally speaking, a suitable CO2 adsorbent needs to have high selectivity and adsorption capacity, adequate adsorption/desorption kinetics, stability after several adsorption/desorption cycles, and good chemical and mechanical stability.
Among many CO2 adsorbents, porous solid adsorbents have good application prospects because of their low adsorption enthalpy and easy recycling. The traditional porous adsorbents for CO2 capture mainly include activated carbon, zeolite, silica gel, activated alumina, and so on[45-48]. Zeolite, a common solid adsorbent, is a porous silica-aluminate material with a pore size between 5 Å and 12 Å[49-51]. Among them, zeolite 13X is the most widely studied adsorbent, with a specific surface area of 726 m2 g-1, a pore volume of 0.25 cm3 g-1, and a CO2 adsorption capacity of 16.4 wt% (0.8 bar) at room temperature, which can be used as a benchmark for solid adsorbents[52,53].
Another class of solid adsorbents is carbon-based adsorbents, including activated carbon, carbon molecular sieves, and carbon nanotubes, which have been used for different forms of CO2 separation. The common activated carbon has an inorganic porous structure, high surface area, and high CO2 adsorption capacity, and it can be generated through resin and other pyrolysis processes, which is a low-cost and highly available adsorbent[54,55]. Even in an environment with water vapor, activated carbon can maintain its structure without being destroyed and has high adsorption stability. However, activated carbon has lower CO2 adsorption capacity at low pressures and poor adsorption selectivity for different gases due to the absence of an electric field generated by cations on the activated carbon surface. To sum up, these traditional adsorption technologies and adsorbents need to be further improved to enhance their ability of CO2 capture and separation.
MOFs are the most representative new porous materials and promising adsorbents, which have attracted extensive attention in gas separation applications[56,57]. As a porous adsorbent with a framework structure formed by organic ligands bridging metal ion nodes, the MOF has a very high surface area, ultra-high porosity, flexibility of the porous structure, and diversity of surface functional groups due to the presence of organic ligands and is easy to be chemically modified. These advantages make MOFs exhibit great potential for CO2 capture and storage[58-60].
CO2 capture performance parameters
Compared with other solid materials, the greatest advantage of MOFs lies in their ability to precisely fine-tune their pore size through the modulation of ligand size. At the same time, the pore environment can be modified by modifying the functional groups on the metal ions (clusters) or ligands to enhance the interaction force with the guest molecules, thus achieving the separation of different gas molecules[61-64]. There have been several reviews on MOFs for gas separation applications, and they have made great progress in adsorptive separation applications in the past few years. However, there are still some limitations. To address the limitations of MOFs, a series of studies have been conducted in recent years on improving their adsorption and separation capacities, expanding new structures, novel functionalization pathways, and adopting hybrid systems and techniques[65]. In addition, studies exploring the adsorption mechanism of MOFs and the improvement of their adsorption capacity in moist environments have gradually become the focus of attention[14,66]. An adsorbent suitable for capturing CO2 from flue gas should consider the following performance parameters.
The adsorption capacity of CO2
This is a key criterion for evaluating the performance of solid sorbents and represents the quantity of sorbent required for a given load, as well as the adsorbent bed size, which is deemed to be a key factor in determining the energy requirement in the regeneration step. In addition, the amount of CO2 adsorbed is related to its partial pressure in the gas phase. The specific adsorption of CO2 indicates the ability of the MOF material to adsorb CO2
The selectivity of CO2
It represents the adsorption ratio of the adsorbent for CO2 to other gases (usually used for post-combustion capture and natural gas upgrading). The sorption selectivity of a gas mixture for CO2 can be estimated quantitatively by means of a single-component gas sorption isotherm or ideal adsorption solution theory (IAST). The CO2 selectivity of materials is primarily due to the following aspects (the relevant parameters are shown in Table 1): (1) Selectivity based on pore size screening (molecular sieve effect). Due to the different kinetic diameters of gas molecules of each component in the gas mixture, CO2 can be effectively separated from the gas mixture by precisely adjusting the pore size of the material; (2) Selectivity based on adsorption (thermodynamic separation), i.e., separation based on the interaction forces between different gas molecules and the material surface and; (3) Selectivity based on diffusion effects, i.e., to separate the gas mixture according to the different diffusion rates of different gases in the material[5,67].
Physical properties of common gas molecules coexisting with CO2
| Gas molecules | Dynamic diameter (Å) | Size (Å) | Boiling point (K) | Polarity (10-25 cm3) |
| N2 | 3.64 | - | 77.35 | 15.3 |
| H2 | 2.89 | - | 20.38 | - |
| H2O | 2.65 | - | 373 | 14.8 |
| CO2 | 3.3 | 3.18 × 3.33 × 5.36 | 194.75 | 29.11 |
| C2H2 | 3.3 | 3.32 × 3.34 × 5.70 | 188.4 | 33.3-39.3 |
| CH4 | 3.76 | 3.83 × 3.94 × 4.10 | 111.6 | 25.93 |
The adsorption enthalpy of CO2
Adsorption enthalpy is another key parameter for evaluating the performance of the storage of CO2 by physical adsorption. It represents the strength of the interaction between the adsorbent and the adsorbate molecules. Moreover, it is an indicator of the energy required to regenerate a solid adsorbent, and the magnitude of the adsorption enthalpy clearly affects the cost of the adsorbent regeneration process. If the adsorption enthalpy is too high, the material binds CO2 too strongly, requiring a large amount of energy to break the framework-CO2 interaction, thereby increasing the regeneration cost. Conversely, very low adsorption enthalpy is undesirable. While regeneration costs will be lower, the captured CO2 will be less pure, resulting in lower adsorption selectivity and a larger adsorption bed size[68-70]. Typically, the adsorption enthalpy of MOFs is in the range of 20-50 kJ mol-1, which is comparable to other physical adsorbents (such as zeolites). Table 2 shown some MOF-based sorbents with their CO2 uptake capacity and Qst.
MOF-based sorbent and related CO2 uptake capacity at 298 K
| Materials | BET surface area (m2/g) | Pressure (bar) | Capacity (mmol g-1) | Qst (kJ mol-1) | Ref. |
| Fe-dbai | 1,280 | 1 | 6.4 | 23.5 | [100] |
| Cu(adci)-2 | 805 | 0.15 | 2.01 | 27.5 | [110] |
| NKU-521 | 1,100 | 1 | 6.21 | 41 | [119] |
| MUF-16(Mn) | 214 | 1 | 2.31 | 37 | [113] |
| MUF-16(Ni) | 204 | 1 | 2.25 | 32 | [113] |
| ZnDatzBdc | 303 | 1 | 2.05 | - | [125] |
| NJU-Bai52 | 1,908 | 0.0004 | 0.013 | 18.1 | [128] |
| NJU-Bai53 | 1,844 | 0.0004 | 0.64 | 17.5 | [128] |
The experimental adsorption enthalpy (Qst) was applied to assess the strength of the bond between the adsorbent and the adsorbate and was defined as:
The adsorption enthalpy, Qst, is determined using the pure component isotherm fits using the Clausius-Clapeyron equation, where T(K) is the temperature, p(kPa) is the pressure, and R is the gas constant.
The stability of the CO2 adsorbent
In order to reduce operating costs and operational difficulties, solid adsorbents must be able to be used in a wide range of industrial environments and show good stability under fume conditions, under adsorption operating conditions, and during multi-cycle adsorption regeneration. Particular attention must be paid to the stability of the adsorbent in the presence of water vapor. In addition, chemical and mechanical stability are equally important[71].
The adsorption/desorption kinetics of CO2
Sorption-regeneration cycle times are largely dependent on the kinetic properties of the CO2 adsorption-desorption curves measured in breakthrough experiments. The ability to effectively reduce the cycle time and the amount of adsorbent, thereby lowering the cost of CO2 separation, is the first parameter to be considered in selecting the CO2 adsorbent. Adsorbents that adsorb and desorb CO2 in a relatively short period of time become the preferred choice.
The cost of adsorbent material
This is an essential ingredient in choosing an adsorbent material. Owing to the high preparation cost, many adsorbents with excellent adsorption properties are not successfully used in industry. Therefore, the preparation of materials with good adsorption properties at low cost is considered to be the main goal of researchers in the field of CO2 capture.
Based on the above elaboration of CO2 capture performance parameters, the quantitative assessment of the CO2 capture capacity of adsorbents mainly refers to the following data: (1) The adsorption capacity of CO2 at 15 kPa is greater than 50 STP cm3 g-1; (2) IAST selectivity (CO2/N2 = 15/85) is greater than 500; (3) Good thermal stability, the structure will not collapse before the temperature is higher than 300 °C; (4) Good chemical stability, the structure remains stable in most organic solvents; (5) Qst < 40 kJ mol-1.
Research progress of MOFs for CO2 capture
As novel porous materials, MOFs were initially proposed by Prof. Omar M. Yaghi and have been extensively researched by scientists[72-77]. They are formed from inorganic metal ions or clusters and organic ligands that are connected through coordination bonds with varying degrees of connectivity. In contrast to conventional inorganic porous materials, such as porous silicates and molecular sieves, MOFs possess a remarkably adaptable structure. Different structures and characteristics of MOFs are built by choosing metal nodes with varying activities and a diverse range of organic ligands[78-80]. Furthermore, they enable specific function-oriented compositions. By utilizing various trapping mechanisms, including molecular sieve separation, host-guest interaction, and kinetic diffusion, MOFs with distinct pore sizes ranging from micropore to mesopore can be conveniently synthesized by modifying the length of ligands or functionalizing inorganic nodes and ligands, resulting in MOFs with unique properties. As novel crystalline porous materials, MOFs possess significantly higher specific surface area and porosity compared to other porous materials (with a specific surface area of up to 10,000 m2 g-1 and porosity of 90%), providing substantial scope for the development in gas storage[81,82], adsorption and separation[83], catalysis[84], sensor[85], and other areas.
The ability of MOFs to capture CO2 from varying gas mixtures depends on their inherent properties and the attributes of the gas mixtures. Over the past two decades, diverse topological structures and function-oriented MOFs have been synthesized, leading to the formation of various branches of materials, including iso-reticular MOFs (IRMOFs), zeolitic imidazolate frameworks (ZIFs), materials of institute Lavoisier frameworks (MILs), and porous coordination networks (PCNs), etc.[86-89]. Different branches possess specific characteristics to cater to distinct applications. Currently, several relatively mature strategies [Figure 2] have been applied to synthesize CO2 capture-oriented MOFs[90-92].
Figure 2. Schematic representation of MOF performance parameters and state-of-the-art CO2 capture strategies.
Functionalized modification strategy
The -NH2 functional group is widely utilized in various adsorbent materials due to its strong attraction of CO2 to the amine group, which gives the amine molecule higher adsorption and selectivity for CO2. Moreover, numerous polar functional groups, including halogen atoms, hydroxyl, carboxyl, cyano, and nitro, have been demonstrated to influence the adsorption ability of CO2 in MOFs[93-95].
Diamine-functionalized MOFs in the form of diamine-Mg2(dobpdc) (dobpdc4- = 4,
Figure 3. Depiction of the formation of ammonium carbamate chains in diamine-Mg2(dobpdc) upon cooperative CO2 adsorption. Reproduced with permission from Dinakar et al.[96]. Copyright 2021 American Chemical Society.
It has been shown that some specific sites of MOFs can effectively capture CO2, including unsaturated metal sites (UMSs) and Lewis base sites (LBSs), such as amines, pyridines, sulfones, and amides. UMSs are capable of establishing potent electrostatic interactions with CO2 and have a high CO2 capture capacity. However, the ubiquitous water molecules tend to coordinate with UMSs in a competitive manner, resulting in a significant reduction in the ability of CO2 adsorption. Regarding LBSs, compared with -NH2, the amide functional group exhibits a robust attraction towards CO2 due to the existence of two binding sites, carbonyl (CO-) and amine (NH-), leading to superior CO2 adsorption and selectivity[97-99]. In addition, MOFs modified by amide functional groups tend to be more stable.
Fe-dbai (dbai = 5-(3,5-Dicarboxybenzoylamino) isophthalic acid) combines two specific functional sites, UMSs and amide functional groups. Its CO2 adsorption capacity is measured at 6.4 mmol g-1, while its
Figure 4. Adsorption behavior and experimental column breakthrough curves of Fe-dbai. Reproduced with permission from
Amino acid (AA)-modified MOFs also show great potential for CO2 capture applications. Modification of MOF-808 with 11 different AAs resulted in a series of MOF-808-AA structures [Figure 5]. Under fume conditions, MOF-808 functionalized with glycine and DL-lysine (MOF-808-Gly and MOF-808-DL-Lys) was observed to exhibit the greatest CO2 adsorption capacity. The increased CO2 capture efficiency in the presence of water was detected and analyzed by single-component adsorption isotherms, CO2/H2O dichotomy isotherms, and dynamic breakthrough measurements. This study enhances our comprehension of CO2 capture in MOFs by uncovering the mechanism in which amine groups, firmly attached to the MOF structure, generate molecules within the pores that facilitate the adsorption and desorption of CO2 at relatively low temperatures without requiring any heating[101].
Figure 5. Structure of MOF-808-AA and structural schemes of the coordinatively loaded amino acids. Reproduced with permission from Lyu et al.[101]. Copyright 2022 American Chemical Society.
Among physisorption materials, anion-functionalized MOFs are novel porous materials composed of metal moieties, organic linkers, and inorganic anions[102,103]. In recent years, anionic-functionalized MOFs have gradually made their presence felt in the field of CO2 capture. The reticular design approach can effectively regulate the pore chemistry of anionic-functionalized MOFs by utilizing molecular building units. As previously reported by Bhatt et al., NbOFFIVE-1-Ni and SIFSIX-3-Cu exhibit CO2 adsorption capacities of 1.3 and 1.2 mmol g-1 at a low concentration of 400 ppm and 298 K, respectively[104]. Their study also shows that reducing the pore size of the porous adsorbent facilitates enhanced interaction between the CO2 molecules and the main framework, resulting in high CO2 uptake at lower pressures.
ZU-16-Co is an anion-functionalized MOF with fine-tuned pore chemistry featuring one-dimensional (1D) pores modified by enriched F atoms that can effectively trap CO2 at concentrations of 400-10,000 ppm. Highly organized Lewis basic sites of anions limited to the ultramicroporous pores substantially enhance the ability to bind CO2 [Figure 6]. This work clarifies the structure-function relationship of ZU-16-Co in capturing CO2 and demonstrates its suitability for decarbonization at low concentrations[105].
Figure 6. (A) Schematic representation of the construction and the pore structure of ZU-16 (TIFSIX-3) materials with pyrazine linker; (B) CO2 adsorption isotherms on various anion-functionalized ultramicroporous materials at 298 K; (C and D) CO2/N2 (1/99, flow rate:
Two polar sulfonated oxygen-rich 3D MOFs, {[Zn2(TPOM)(3,7-DBTDC)2] 7H2O·DMA}n (1) and
Figure 7. Single-crystal X-ray structure of 1 (A) and 2 (B). Reproduced with permission from Chakraborty et al.[106]. Copyright 2020 American Chemical Society.
The pore windows and pore sizes of MOFs are made up of both organic and inorganic structural blocks. Therefore, the pore size of MOFs can be adjusted by changing the type of organic and inorganic structural blocks, allowing the pore structure of MOFs to vary considerably in size, which is one of the key reasons for the wide variety of MOF materials currently available. Due to the wide range of pore sizes of MOFs, they show great potential for different kinds of gas capture applications[108,109]. Selective adsorption of CO2 can be achieved by using large linkers, short ligands, interpenetrating networks, and smaller metal molecules.
A novel copper-based ultramicroporous MOF, Cu(adci)-2 (adci = 2-amino-4,5-dicyanoimidazole), was proposed by Jo et al.[110]. This MOF is a CO2 capture-oriented physical adsorbent synthesized by two strategies: performing aromatic amine functionalization and introducing ultramicropores. The Cu(adci)-2 structure has one-dimensional square channels where all of the auxiliary ligands, particularly the NH2 group at the 2 position of the imidazole ring, are oriented in the identical direction in each channel so that pairs of NH2 groups face away from each other along contrary sides of the channel walls. cu(adci)-2 shows higher CO2 adsorption capacity (2.01 mmol at 298 K and 15 kPa g-1) but a lower adsorption enthalpy at zero coverage (27.5 kJ mol-1). It showed good selectivity and easy regeneration under both dry and humid conditions [Figure 8].
Figure 8. (A) Rietveld plot of desolvated Cu(adci)-2; (B) Perspective views of the refined structure of Cu(adci)-2 along the c (left) and b (right) axes; (C) Top and side views of a 1D channel of Cu(adci)-2. Reproduced with permission from Jo et al.[110]. Copyright 2022 American Chemical Society.
CALF-20 consists of 1,2,4-triazole-bridged zinc(II) ion layers supported by oxalate ionic pillars forming a 3D lattice and a 3D pore structure [Figure 9]. The crystallographically unique zinc center is five-coordinate with a distorted triangular bipyramidal geometry. The competitive separation on CALF-20 shows not only preferential physisorption of CO2 below 40% RH but also inhibition of water adsorption by CO2, which is confirmed by computational modeling. Furthermore, CALF-20 facilitates industrial-scale CO2 capture in a cost-effective and reliable manner[111]. This shows that the reasonable addition of anionic column bracing can effectively inhibit water adsorption, which, in turn, makes the adsorbent exhibit an excellent CO2 capture capacity.
Figure 9. (A-C) Single-crystal structure of CALF-20; (D) Powder X-ray pattern simulated from the single-crystal structure (top) and obtained experimentally. Reproduced with permission from Lin et al.[111]. Copyright 2021 American Association for the Advancement of Science.
Efficient and sustainable CO2 capture can be achieved by porous physical adsorbents with high void fraction whose sizes and electrostatic potentials complementary to CO2 molecules[112]. Qazvini et al. proposed a strong, recoverable, and affordable adsorbent called MUF-16 [Figure 10][113]. MUF-16(Co), MUF-16(Ni), and MUF-16(Mn) were prepared by mixing 5-amino-m-m-phthalic acid (H2aip), a cheap, commercially available ligand, with cobalt (II), nickel (II), or manganese (II) salts in methanol. Through static adsorption curves, IAST, and density functional theory calculations, it is determined that the one-dimensional channel of MUF-16 can capture CO2 with high affinity while demonstrating weaker affinities for other competitive gases such as CH4, C2H2, C2H4, C2H6, C3H6, and C3H8. Therefore, MUF-16 has high CO2 adsorption selectivity. The selectivity of MUF-16 to CO2/CH4 and CO2/C2H2 is measured at 6,690 and 510, respectively.
Figure 10. (A-D) Synthesis and structure of MUF-16 materials; (E) Volumetric adsorption (filled circles) and desorption (open circles) isotherms of CO2 at 293 K and for MUF-16 (black), MUF-16(Mn) (red), and MUF-16(Ni) (blue); (F) Adsorption enthalpy (Qst) calculated for CO2 binding to MUF-16 (black), MUF-16(Mn) (red), and MUF-16(Ni) (blue) as a function of CO2 uptake. Reproduced with permission from Qazvini et al.[113]. Copyright 2021 Springer Nature.
Open metal site modification strategy
Besides the functionalization of MOFs, metal sites have an important impact on enhancing the capacity and selectivity of CO2 relative to other gases. UMSs are usually partially positively charged, and these sites show an affinity for larger quadrupole moments and greater polarizability for CO2 compared to N2. It is these open sites that lead to high CO2 uptake. Furthermore, the difference in intensity between CO2 and other gas molecules is the driving force for CO2 capture[114-116].
MIL-101 has two dissimilar mesopores and distinct metal sites in a single local pore. Shin et al. demonstrated by adsorption isotherm combined with in situ crystallographic analysis that substrate-adsorbate interactions influence the initial adsorption and pore coalescence steps[117].
Unsaturated alkali metal sites have been reported to be anchored in MOFs by tetrazolium-based patterning to improve gas affinity[118]. In NKU-521 (NKU denotes Nankai University), Li et al. effectively embedded K+ cations into the trinuclear Co2+-tetrazolium coordination pattern[119]. The embedded K+ sites were exposed in the pores of NKU-521 by dehydration, and the Qst of CO2 increased to 41 kJ mol-1. The K+ cations actually act as gas traps and increase the CO2-framework affinity, as measured by the Qst, by 24%. Furthermore, the effect of unsaturated alkali metal sites in MOFs on hydrocarbon separation was investigated. IAST calculations and breakthrough experiments showed that the exposed K+ sites greatly improved the CO2 capture and separation performance of this MOF [Figure 11].
Figure 11. Structural change of the embedded K+ from H2O coordinated state to the exposed state as CO2 traps for the preferential binding of CO2. Reproduced with permission from Li et al.[119]. Copyright 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
UMSs and adsorbent polarity play an important role in CO2 adsorption. MIL-88 was selected as the prototyping framework to verify the above strategy[120]. By introducing the C3 symmetry of the second ligand 2,4,6-tri(4-pyridyl)-1,3,5-triazine (tpt), the initial hexagonal 1D pore of the MIL-88 is split into numerous hexagonal cages of a certain length. As a direct result, MIL-88 loses metal vacancies and is replaced by split ligands. Moreover, the framework becomes more rigid, and there is no respiration effect before and after gas adsorption. The introduction of the second ligand (tpt) not only provides more action sites but also enhances the interaction area between objects. In addition, the group also modifies the terephthalic acid that constitutes the framework, introduces -OH and -NH2 groups, and increases the interaction sites between gas molecules and the framework. The CO2 adsorption test shows that CPM-33b with tpt and -OH introduced has the highest CO2 adsorption value compared to the existing MOFs without metal vacancies, which is comparable to the adsorption effect of MOF-74-Ni [Figure 12]. This study provides a new idea for MOFs to improve gas adsorption performance and is expected to achieve greater breakthroughs in fuel molecule adsorption.
Figure 12. (A and B) Illustration of pore space partition through symmetry-matching regulated ligand insertion; (C-F) Gas sorption study on compounds CPM-33a and CPM -33b. Reproduced with permission from Zhao et al.[120]. Copyright 2015 American Chemical Society.
Other functionalization
In addition to these common CO2 capture strategies, scientists have also explored other ways to efficiently capture CO2. In a typical Langmuir-type isotherm, bulk CO2 adsorbents cannot be regenerated during desorption because the adsorption gain decreases with increasing temperatures. Instead, adsorbents with S-shaped CO2 isotherms are preferable. Some flexible MOFs can display such S-shaped CO2 equivalent due to the structural switch from the CP (close-phase) state to the OP (open-phase) state[121-123]. Furthermore, as an individual guest molecule has its own gate opening pressure, this difference allows for high selectivity in gas mixtures, i.e., the target molecule can open the gate while others cannot[124]. Therefore, flexible MOFs with S-shaped isotherms can be used as potential carbon capture adsorbents with good operability and high selectivity for CO2.
ZnDatzBdc (Datz = 3,5-diamine-1,2,4-triazolate, Bdc = 1,4-benzenedicarboxylate) is a flexible MOF for highly selective capture of CO2 [Figure 13]. X-ray diffraction studies confirmed a convertible structure conversion between its OP and CP states. Importantly, ZnDatzBdc exhibits an S-shaped CO2 isotherm, yielding appreciable CO2 workability of 94.9 cm3 cm-3 under typical PVSA operations at 273 K, superior to most reported flexible MOFs[125].
Figure 13. (A) Single-component CO2 isotherms on ZnDatzBdc up to 100 kPa and varied temperatures; (B) adsorption isotherms of CO2, N2, and CH4 up to 100 kPa at 273 and 298 K; (C) CO2 working capacities for the step-shaped isotherm of ZnDatzBdc and the simulated Langmuir isotherm from the CO2 adsorption data in the open phase, for a cycle of adsorption at 100 kPa and desorption at
Mechanochemistry at the chemical reaction level mainly refers to the application of mechanical energy to condensed substances, such as solids and liquids, by means of shear, abrasion, impact, and extrusion to induce changes in their structure and physicochemical properties and to induce chemical reactions. Unlike ordinary thermochemical reactions, mechanization, the driving force of the reaction, is mechanical energy rather than thermal energy; thus, the reaction can be completed without high temperature, high pressure, and other harsh conditions. It has been developing rapidly. This approach not only provides a green and energy-efficient route for chemical transformations but also offers more possibilities for the expanded preparation of materials[126]. Ultramicroporous MOFs with negatively charged anionic columns, such as
Figure 14. (A and B) Adsorption isotherms of CO2, CH4, and N2 on ZU-36 materials at 298 K. (C) Comparison of the CO2 uptake on various materials at 400 ppm. (D) IAST selectivity of CO2/N2 (15/85) and CO2/CH4 (50/50) on ZU-36 materials; (E) Qst value of CO2 on
A winning path to high levels of connectivity MOFs was proposed by Cairns et al. in 2007 by using metal-organic polyhedra (MOPs) as supramolecular building blocks (SBBs)[127]. NJU-Bai52 and NJU-Bai53, prepared by a pure-supramolecular-linker (PSL) approach, are two kinds of high-connected isomeric MOFs with a rare (3,3,6,6)-c topology[128]. Among them, TPBTM acts as a 12-connected supramolecular linker connected by the M3O cluster, forming two height-connected linkers. The equilibrium charge on these M3O clusters was delicately tuned from Cl- ions to monodentate hydroxide anions, resulting in a significant ~50-fold increase in the CO2 uptake for NJU-Bai53 (2.74 wt%) compared to NJU-Bai52 (0.74 wt%) at 298 K and 0.4 mbar. At 298 K and 0.15 bar, the CO2 uptake of NJU-Bai53 (7.67 wt%) was greatly increased compared to NJU-Bai52 (0.057 wt%), which is the highest among the reported amide-functionalized MOFs (AFMOFs). In addition,
Figure 15. (A) TPBTM6- ligand self-assembles into PSL by strong π-π stacking and H-bonds, together with Fe3O clusters to construct NJU-Bai52, in which the P-isophthalates form metallamacrocycles and the C-isophthalates bridge these metallamacrocycles; (B) N2 adsorption and desorption isotherms at 77 K of NJU-Bai52 and NJU-Bai53; (C) CO2 adsorption isotherms at 298 K of NJU-Bai52 and NJU-Bai53; (D) CO2 adsorption enthalpies of NJU-Bai52 and NJU-Bai53; (E) breakthrough curves at 298 K of NJU-Bai52 and
CONCLUSIONS
In conclusion, a great deal of CO2 capture research has been performed on MOFs in the past few decades. This is due to their special properties, such as large pore volume, high surface area, maintainability, structural diversity, etc. This review systematically describes several strategies that can be applied to design and synthesize CO2 capture-oriented MOFs, such as tuning the pore size window, functional group modification, and active site insertion. The emergence of these synthetic strategies offers enormous possibilities for the use of MOFs in practical applications in the area of CO2 capture and separation. Regardless of these strategies, it is imperative that certain characteristics of the original MOF are considered during the design phase, including the original functional groups, crystal structures, and acid and base properties of the MOF.
DECLARATIONS
Authors’ contributionsConceptualization, investigation, and writing-original draft: Sun M
Editing: Wang X, Gao F, Xu M
Writing-review & editing, supervision, and funding acquisition: Fan W, Xu B, Sun D
Availability of data and materialsNot applicable.
Financial support and sponsorshipThis work was supported by the National Natural Science Foundation of China (NSFC, Grant Nos. 22201305, 22275210), the Fundamental Research Funds for the Central Universities (22CX06024A, 23CX04001A), and the Outstanding Youth Science Fund Projects of Shandong Province (2022HWYQ-070).
Conflicts of interestAll authors declared that there are no conflicts of interest.
Ethical approval and consent to participateNot applicable.
Consent for publicationNot applicable.
Copyright© The Author(s) 2023.
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Sun M, Wang X, Gao F, Xu M, Fan W, Xu B, Sun D. Synthesis strategies of metal-organic frameworks for CO2 capture. Microstructures 2023;3:2023032. http://dx.doi.org/10.20517/microstructures.2023.32
AMA Style
Sun M, Wang X, Gao F, Xu M, Fan W, Xu B, Sun D. Synthesis strategies of metal-organic frameworks for CO2 capture. Microstructures. 2023; 3(4): 2023032. http://dx.doi.org/10.20517/microstructures.2023.32
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Sun, Meng, Xiaokang Wang, Fei Gao, Mingming Xu, Weidong Fan, Ben Xu, Daofeng Sun. 2023. "Synthesis strategies of metal-organic frameworks for CO2 capture" Microstructures. 3, no.4: 2023032. http://dx.doi.org/10.20517/microstructures.2023.32
ACS Style
Sun, M.; Wang X.; Gao F.; Xu M.; Fan W.; Xu B.; Sun D. Synthesis strategies of metal-organic frameworks for CO2 capture. Microstructures. 2023, 3, 2023032. http://dx.doi.org/10.20517/microstructures.2023.32
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