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Effective formaldehyde capture by green cyclodextrin based metal-organic framework Lu Wang, Xiang-Yong Liang, Zhi-Yi Chang, Li-Sheng Ding, Sheng Zhang, and Bang-Jing Li ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b16520 • Publication Date (Web): 14 Dec 2017 Downloaded from http://pubs.acs.org on December 14, 2017

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ACS Applied Materials & Interfaces

Effective Formaldehyde Capture by Green Cyclodextrin based Metal-Organic Framework Lu Wang,a,c Xiang-Yong Liang,a,c Zhi-Yi Chang,a,c Li-Sheng Ding,a Sheng Zhang,*b Bang-Jing Li*a a. Key Laboratory of Mountain Ecological Restoration and Bioresource Utilization, Chengdu Institute of Biology Chinese Academy of Sciences, Chengdu, 610041, China. b. State Key Laboratory of Polymer Materials Engineering, Polymer Research Institute of Sichuan University Sichuan University, Chengdu, 610065, China. c. University of Chinese Academy of Sciences, Beijing, 100049, China. Corresponding authors: [email protected], [email protected] KEYWORDS: Metal-organic framework; Cyclodextrin; Formaldehyde; Host-guest interaction; Hydrogen binding

ABSTRACT

A kind of metal-organic framework made from γ-cyclodextrin (γ-CD) and potassium ions were explored as excellent formaldehyde (HCHO) absorbents. The adsorption capacity and speed of γ-CD-MOF-K are both about 9 times higher than those of activated carbon, which attribute to the porous structure and synergistic effect of hydrogen bonding and host-guest interactions.

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The indoor air quality plays very important role in human health since people spend more than 80% of their time in indoors. Formaldehyde (HCHO) is a major indoor pollutant, since it is a crucial chemical of the adhesive used for plywood, particleboard and wall papers, commonly used in construction and furnishing1. In China, for example, more than 69.4% of all newly built or remodelled houses have indoor formaldehyde levels exceeding that national standard (0.1 mg/m3). The flammable and colorless gas HCHO irritates the eyes and upper airway mucosa2. It is well known that long-term exposure to HCHO can cause many adverse effects including nasopharyngeal carcinoma, pregnancy syndrome, encephaloma, leukemia and so on3. In terms of the levels of HCHO and the number of people exposed, the removal HCHO are of serious concern. There have been many studies suggesting that the common ways for the removal of HCHO are air exchange method, physical adsorbing4-5, chemical reaction6 and so on. Taking the practicality and cost into consideration, there are two efficient and convenient methods for the removal of HCHO, using a chemical reaction and physical adsorption. Photo-catalytic degradation of HCHO is the main chemical reaction for removal of HCHO6. However, this kind of oxidation reaction is in the need of UV light source, making that the practical result is poor in indoor environment. Adsorption is a more convenient and more effective approach to remove HCHO in actual environment. A lot of physical adsorbents have been designed, such as aluminum oxide7, activated carbon8, hydroxyapatite9 and so on. Nevertheless, most of these adsorbents need extra modification to be connected with polar groups, since HCHO is a typical polar molecule. It is emergent to find methodology for high effective removal HCHO in indoor environment.


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Metal−organic frameworks (MOFs) are a class of crystalline porous materials, composing of metal ions connected by organic linkers in an orderly manner10-13. They have received increased scientific and technological interests by the researchers, because of large surface areas, rich organic functionalities and tunable porosity14. They have great wildly potential applications including gas storage15, separation16-19, chemical sensing20, catalysis21 and so on. In recent years, MOFs also have showed potential for use in air purification of toxic gases.22-23 Yaghi’s group22synthesized a series of MOFs with different metal centers for harmful gases adsorption. Waltonet.al23 modified four MOFs with different functional groups for the adsorption of ammonia. However, mentioned above MOFs are mostly synthesized by non-renewable petrochemical, heavy metal and toxic solvents. Furthermore, the study about MOF for removal HCHO is rare. Lately, Stoddart and his co-workers discovered a series of MOFs called CD-MOFs24-30, which were built by cyclodextrin (CD), and alkali metal ions. These CD-MOFs take advantages of porous structures, high local concentrations of the hydroxyl groups and “green” properties. Stoddart et.al25 has explored γ-CD-MOF for the CO2 capture. In this work, we studied the capability of CD-MOFs for removal of HCHO. According to our experiment results, it was found that γ-CD-MOF showed selective adsorption for HCHO with high adsorption capability and speed, since HCHO can be adsorbed not only in the cavities of γ-CD through host-guest interactions but also on the pores in the framework through hydrogen bonding with hydroxyl groups. Since the CD-MOFs prepared from renewable sources and nontoxic metal salts, it is special interest to apply them in the air purification. We prepared three kinds of potassium based CD-MOFs, α-CD-MOF-K, β-CD-MOF-K and γ-CD-MOF-K according to the previous reported, respectively24-27. The XRD patterns of CD-


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MOFs were totally different from the raw CDs (Figure S2b, S3b and S4b), and matched the results of CD-MOFs reported by previous literatures27-30 (Figure S11, S12 and S13). To further confirm the structure of CD-MOFs, the IR and XPS results were showed in Figure S14 and Figure S15. Scanning electron microscopic (SEM) images of three kinds of CD-MOFs were uniform crystals (as shown in FigureS2a, S3a, S4a). According to the above results, we can conclude that CD-MOFs were successful prepared and the structures were corresponding to the reported products. In this work, the adsorption behavior was characterized by the concentration-time curve, the Y-axis was the concentration of HCHO and X-axis represented the detection time. Figure 1a showed the HCHO adsorption behavior of three kinds of CD-MOF-Ks and CDs at 293 K and 1atm. It can be seen that all of CDs showed modest HCHO adsorption ability, indicating that the cavities of CDs were able to form inclusion complexes with HCHO. The adsorption speed was γCD>β-CD>α-CD. The HCHO adsorption capability of CD-MOFs were better than that of CD molecules, suggesting that the open and porous structure of MOFs helped the HCHO adsorption. It has been reported that α-CD-MOF-K exhibited a left-handed helical chiral layer structure with big pores (11 Å diameter) and small pores (7 Å diameter); β-CD-MOF-K contained bowl-like pore (6 Å) and double channels (size ca. 5 Å); And γ-CD-MOF-K was body-centered cubic with pores (7.8 and 4.2 Å).The sizes of all of the pores in CD-MOF were larger than the size of HCHO. It should be noticed that γ-CD-MOF-K showed much high adsorbing speed and capacity than the other kinds of materials.0.48 mg/m3 HCHO were almost adsorbed completely in 15 min by γ-CD-MOF-K (The limit of detection was 0.001mg/m3), while other materials took over 1 h to adsorb only half of HCHO, implying that the distinctive features of γ-CD-MOF-K made them to show excellent HCHO adsorption capacity.


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Figure 1. (a) The HCHO adsorption curves of α-CD-MOF-K, β-CD-MOF-K, γ-CD-MOF-K, αCD, β-CD and γ-CD at 293 K and 1 atm. (b) The adsorption curves of activated carbon and γCD-MOF-K at 293 K and 1 atm. Figure 1b showed the adsorption curves of HCHO at 293 K for γ-CD-MOF-K and activated carbon. It can be seen that γ-CD-MOF-K showed much high adsorbing speed and capacity than activated carbon. Activated carbon required more than 60 min to reach equilibrium and only adsorbed 50% of formaldehyde. While using γ-CD-MOF-K as absorbents, the concentration of HCHO can rapidly drop from 0.487 mg/m3 to 0.001 mg/m3 in 15 minutes. Furthermore, γ-CDMOF-K showed adsorption capacity of 36.71 mg/g under saturated HCHO steam condition, which was nine times higher than activated carbon. The SEM and XRD of γ-CD-MOF-K after adsorption of formaldehyde were shown in Figure S8. It can be seen that the structure of γ-CDMOF-K retained its integrity after long-time HCHO adsorption. Besides the porous structure and host-guest interactions between HCHO and γ-CD, we suppose that hydrogen bonding between HCHO and hydroxyl groups on the framework also contribute to the excellent HCHO adsorption capability of γ-CD-MOF-K. As shown in Figure 2a, we compared the HCHO adsorption behavior of three kinds MOF, γ-CD-MOF-K, UiO-66OH which contained high hydroxyl groups concentration but without CD, and ZIF-8 without


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hydroxyl groups and CD. It can be seen that UiO-66-OH showed better adsorption ability than ZIF-8 and the γ-CD-MOF-K showed the best adsorption ability. Therefore, we suppose that the γ-CD-MOF-K adsorb HCHO not only in the cavities of γ-CD through host-guest interactions, but also on the surface of γ-CD through hydrogen bonding (shown as scheme 1). The hydroxyl group concentration in CD-MOF is γ-CD-MOF-K >β-CD-MOF-K>α-CD-MOF-K. It can be seen that the HCHO adsorption capacity of CD-MOF increased with the increase of hydroxyl groups. γCD-MOF-K showed best HCHO adsorption capacity. Figure 2b showed the adsorption isotherms of benzene, phenylethylene, HCl and sulfur dioxide on γ-CD-MOF-K at 293 K and 1 atm. It can be seen that the γ-CD-MOF-K showed much better adsorption capacity for polar compound (formaldehyde, HCl, and sulfur dioxide) than for nonpolar compound (phenylethylene and benzene). These results suggested that hydroxyl groups located on γ-CD are capable of forming hydrogen bonding with polar gases.

Scheme1. The structure of γ-CD-MOF and HCHO-γ-CD-MOF.


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Figure 2. (a)The HCHO adsorption curves of γ-CD-MOF-K, ZIF-8, and UiO-66-OH at 293 K and 1 atm.(b) Different kinds of gases were adsorbed by γ-CD-MOF-K at 293 K and 1 atm. (c)The corresponding adsorption curves of HCHO adsorption at different relevant temperatures and 1atm. (d) The corresponding adsorption curves of γ-CD-MOF with different metal centers at 293K and 1 atm. It should be noticed that the kinds of metal ions did not affect the HCHO adsorption of γCD-MOF.As shown in Figure 2d, γ-CD-MOF-Cs and γ-CD-MOF-K showed very similar HCHO adsorption behavior (the XRD and SEM of γ-CD-MOF-Cs were shown in Figure S10). According to the XRD pattern of γ-CD-MOF-Cs and γ-CD-MOF-K, the crystal structures of γ-


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CD-MOF-K and γ-CD-MOF-Cs were similar and the crystallinity of γ-CD-MOF-Cs was a little lower than γ-CD-MOF-K. The influence of temperature on the HCHO adsorbing behavior of γ-CD-MOF-K was investigated at 1 atm. As shown in Figure 2c, the concentration of HCHO can sharply decreased from 1.4 mg/m3 to 0.1 mg/m3at 293 K. Then the HCHO adsorbing speed of γ-CD-MOF-K increased with the decrease of temperature. When the temperature was 319 K, the equilibrium concentration of HCHO reached 0.8 mg/m3. The uptake capacity of γ-CD-MOF-K also increased with the temperature decreasing. These results indicated that the adsorption of HCHO was controlled by an exothermic process. The thermodynamic parameters of the γ-CD-MOF-K at different temperature was calculated based on the equilibrium data and was listed on table 1. It can be seen that the absolute value of ∆G0 was very low, which are characteristic for a physical adsorption (40 kJ mol−1). However, when the temperature increased to 318.15 K, the ∆G0 increased to 1.23 KJ/mol and 5.70 KJ/mol for HCHO-γ-CD-MOF-K and HCHO-γ-CD, indicating that the presence of an energy barrier at high temperature, and the adsorption was unspontaneous and less favorable at high temperatures. And the extent of adsorption was decreased in high temperature. The negative values of ∆S0 suggested decreased randomness at the gas/solid interface and no significant changes occur in the internal structure of the γ-CD and γ-CD-MOF-K. The value of ∆H0 was negative, indicating that the adsorption process was an exothermic process. The negative values of∆H0 and ∆S0 for γ-CD and γ-CD-MOF-K supported the fact that the adsorption process was spontaneous.

The Langmuir and Freundlich models were used to fit and exam the adsorption isotherms of HCHO in γ-CD-MOF-K. It was found that the Langmuir isotherm fitted the data well (Figure 3a), suggesting that a monolayer adsorption occurred.


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Table 1. The thermodynamic parameters for adsorption process of γ-CD-MOF-K and γ-CD. Materials

γ-CD-MOF-K

γ-CD

Temperature(K) ∆G0(KJ/mol) 293.15 298.15 308.15 313.15 318.15 293.15 298.15 308.15 313.15 318.15

-4.51 -2.09 -1.55 0.52 1.23 -0.21 -0.21 3.57 3.99 5.70

Kc 6.37 2.32 1.83 0.82 0.63 1.09 0.92 0.25 0.22 0.12

∆H0(KJ/mol)

∆S0(KJ/mol)

-65.84

-0.21

-74.13

-0.26

-

Figure 3. (a) The Langmuir sorption isotherm of γ-CD-MOF-K. (b) Second order reaction rate equation of γ-CD-MOF-K. Besides, the kinetic adsorption data were processed to understand the dynamics of adsorption process in terms of the order of rate constant. Kinetic data were treated with the pseudo-first-order and pseudo-second-order kinetic models. It was found that the pseudo-second-


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order model was suitable to describe the kinetic process (Figure 3b), suggesting that the adsorption process depend on both HCHO and γ-CD-MOF-K. In conclusion, we explored γ-CD-MOF-K as an effective HCHO absorbent with high selectivity, high speed and high capacity. The excellent HCHO adsorption capability of γ-CDMOF-K is believed to be the results of porous structure and synergistic effect of hydrogen bonding and host-guest interactions. It was found that the HCHO adsorption in γ-CD-MOF-K was an exothermic and spontaneous process. It was fit the Langmuir model and depend on both HCHO and γ-CD-MOF-K. In addition, the γ-CD-MOF-K showed added value, such as the facile preparation and “green” property, which make γ-CD-MOF-K as good candidates for the HCHO relative air purification.

Supporting Information. Experimental details and more data as described in the text. AUTHOR INFORMATION Corresponding Author Prof. Bang-Jing Li, Email: [email protected] Prof. Sheng Zhang, Email:[email protected] Author contributions Lu Wang designed experiments, performed, analyzed the results, and drafted the manuscript. Xiang-Yong Liang and Zhi-Yi Chang gave assistants on experiments. Professor Li-Sheng Ding


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Sheng Zhang and Bang-Jing Li supervised the project, helped design the experiments, and revised the manuscript. All authors contributed to the analysis of the manuscript. ACKNOWLEDGEMENTS This work was funded by National Natural Science Foundation of China (Grant Nos. 51573187, 51373174), State Key Laboratory of Polymer Materials Engineering (Grant No. sklpme2017-2-05). REFERENCES 1. Wang, Z.; Liu, J.; Wang, F.; Chen, S.; Luo, H. Yu, X. Size-Controlled Synthesis of ZnSnO3 Cubic Crystallites at Low Temperatures and Their HCHO-Sensing Properties J. Phys. Chem. C 2010, 114, 13577-13582. 2. Noguchi, T.; Fujishima, A.; Sawunyama, P.; Hashimoto, K. Photocatalytic Degradation of Gaseous Formaldehyde Using TiO2 Film Environ. Sci. Technol. 1998, 32, 3831-3833. 3. Photong, S.; Boonamnuayvitaya, V. Enhancement of Formaldehyde Degradation by Amine Functionalized Silica/Titania Films J. Environ. Sci. 2009, 21, 1741-1746. 4. Lin, F.; Zhu, G.; Shen, Y.; Zhang, Z.; Dong, B. Study on the Modified Montmorillonite for Adsorbing Formaldehyde Appl. Surf. Sci. 2015, 356, 150-156. 5. Carter, E. M.; Katz, L. E.; Speitel, G. E.; Ramirez, D. Gas-Phase Formaldehyde Adsorption Isotherm Studies on Activated Carbon: Correlations of Adsorption Capacity to Surface Functional Group Density Environ. Sci. Technol. 2011, 45, 6498-6503. 6. Yu, J. G.; Zhou, M. H.; Cheng, B.; Yu, H. G.; Zhao, X. J.; Ultrasonic Preparation of Mesoporous Titanium Dioxide Nanocrystalline Photocatalysts and Evaluation of Photocatalytic Activity J. Mol. Catal. A-Chem. 2005, 227, 75-80.


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Figure 1. (a) The HCHO adsorption curves of α-CD-MOF-K, β-CD-MOF-K, γ-CD-MOF-K, α-CD, β-CD and γ-CD at 293 K and 1 atm. (b) The adsorption curves of activated carbon and γ-CD-MOF-K at 293 K and 1 atm. 1422x508mm (96 x 96 DPI)



Figure 2. (a) The HCHO adsorption curves of γ-CD-MOF-K, ZIF-8, and UiO-66-OH at 293 K and 1 atm. (b) Different kinds of gases were adsorbed by γ-CD-MOF-K at 293 K and 1 atm. (c)The corresponding adsorption curves of HCHO adsorption at different relevant temperatures and 1atm. (d) The corresponding adsorption curves of γ-CD-MOF with different metal centers at 293K and 1 atm. 169x120mm (300 x 300 DPI)


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Figure 3. (a) The Langmuir sorption isotherm of γ-CD-MOF-K. (b) Second order reaction rate equation of γCD-MOF-K. 1505x587mm (96 x 96 DPI)



Scheme1. The structure of γ-CD-MOF and HCHO-γ-CD-MOF. 169x110mm (300 x 300 DPI)


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