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Metal-Organic Frameworks derivatives for improving the catalytic activity of CO oxidation reaction Wenlan Ji, Zhiling Xu, Pengfei Liu, SUOYING ZHANG, Weiqiang Zhou, Hongfeng Li, Tao Zhang, Linjie Li, Xiaohua Lu, Jiansheng Wu, Weina Zhang, and Fengwei Huo ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b01082 • Publication Date (Web): 15 Mar 2017 Downloaded from http://pubs.acs.org on March 16, 2017

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ACS Applied Materials & Interfaces

Metal-Organic

Frameworks

Derivatives

for

Improving the Catalytic Activity of CO Oxidation Reaction Wenlan Ji#1, Zhiling Xu#1, Pengfei Liu2, Suoying Zhang1,Weiqiang Zhou1, Hongfeng Li1, Tao Zhang1, Linjie Li1, Xiaohua Lu2, Jiansheng Wu1, Weina Zhang1, Fengwei Huo*1 1

Key Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM),

Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing Tech University (NanjingTech), 30 South Puzhu Road, Nanjing 211816, P.R. China 2

State Key Laboratory of Materials-Oriented Chemical Engineering, and College of Chemistry

and Chemical Engineering, Nanjing Tech University, Nanjing 210009, P.R. China

* Corresponding author: [email protected]

ACS Paragon Plus Environment

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ABSTRACT

Metal-Organic Frameworks (MOFs) based derivatives have attracted an increasing interest in various research fields. However, most of reported papers mainly focus on the pristine MOFsbased derivatives, and researches on the functional MOFs-based derivatives composites are rare. Here, a simple strategy was reported to design the functional MOFs based derivatives composites by the encapsulation of the metal nanoparticles (MNPs) in MOFs matrixes (MNPs@MOFs) and the high-temperature calcination of MNPs@MOFs composites. The as-prepared MNPs@metal oxide composites with the hierarchical pore structure exhibited excellent catalytic activity and high stability for CO oxidation reaction.

KEYWORDS: Metal-Organic Frameworks; Functional Derivatives; Hierarchical Structure; Porous Materials; CO Oxidation Reaction

INTRODUCTION Metal–organic framework (MOF) is a class of hybrid functional materials constructed by the coordination of metal ions with organic linkers in an appropriate solvent. Owing to their notable properties such as high surface areas, uniform but tunable cavities, tailorable chemistry and so on,1-3 MOFs composites have received a great deal of interest in various applications such as gas separation,4 gas storage,5 catalysis,6 drug delivery7 and sensing.8 Recently, the research interests of MOFs gradually transfer from the pristine MOFs to MOFs based derivatives9 due to the unstable coordination bond of inorganic metal ions and organic ligands as well as the special porous structure of MOFs. Hence, various inorganic metal materials with high surface area and


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interconnected pores, such as metal oxides,10 metal sulfides,11 metal phosphors,12 multicompositions,13 etc., have been obtained by the transformation of MOFs under suitable calcination conditions. However, most of the researches mainly focused on the pristine MOFsbased derivatives, and few works have been done with respect to the functional MOFs-based derivatives composites. To date, in view of the various applications of MOFs, there have been several strategies to construct the MOFs based derivatives with controllable shape, size, functionality and composition, among which solvothermal method14-15 and high temperature calcinations method16-17 enjoyed a wide popularity. By the solvothermal method which is simple and general, MOFs based derivatives can be successfully obtained through immersing non-metal precursors and MOFs into solvent under suitable calcination conditions, during which process the control of MOFs decomposition and non-metal dissolution remain the problems. By means of high temperature calcination, MOFs and MOFs composites can be easily converted to different MOFs based derivatives, such as metal/metal oxide nanoparticles, carbon–metal/metal oxide hybrids and porous carbons.18-19 The obtained MOFs based derivatives will inherit the porosity and welldefined morphology from MOFs. However, the control of the structure orders in porous carbon and the ingredient of metal/metal oxide nanoporous material should be enhanced in future researches. In addition, the MOFs based derivatives have showed promising applications in various research fields20-24 due to their special morphology and porous structure. It is also noteworthy that the potential applications of MOFs based derivatives can be further extended by imparting various metal nanoparticles (MNPs) within the frameworks matrix25-29 so that the functionalized MOFs based derivatives can exhibit the novel chemical and physical properties endowed by MNPs. Advanced Pt/CeOx/C nanocomposite26 is derived from Ce-containing MOF


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by heat-treatment at 900 °C. Meanwhile, the Pt/CeOx/C exhibited excellent performance in the oxygen reduction reaction. Therefore, it’s necessary to develop the functional MOFs based derivatives for further exploration of their applications. Herein, we reported a facile strategy to prepare the functional MOFs based derivatives composites by the encapsulation of the MNPs in MOFs matrixes (MNPs@MOFs) and the hightemperature calcination of MNPs@MOFs composites under suitable gas condition. The morphology and porosity of corresponding MNPs@metal oxide composites can be adjusted under different gas conditions and temperature rates. The as-prepared MNPs@metal oxide composites as heterogeneous catalyst exhibited excellent catalytic activity and high stability for CO oxidation reaction, probably due to the catalytic activity and good dispersity of MNPs within the porous metal oxides. EXPERIMENT SECTION Synthesis of ZIF-67. In a typical synthesis, 25 ml methanol solution of Co(NO3)2·6H2O (484.3 mg, 66.57 mM), 25 ml methanol solution of 2-methylimidazole (513.13 mg, 0.25 M) were mixed briefly, and the reaction mixture was kept at room temperature for 24 h without stirring. Subsequently, the precipitates were collected by centrifugation, washed with methanol for several times, and then vacuum-dried overnight to obtain ZIF-67. Synthesis of PVP-stabilized Pt NPs.30 2.9 nm PVP-stablized Pt NPs were fabricated by refluxing a mixed solution of 180 ml methanol, 133 mg polyvinylpyrrolidone (PVP) (Mw≈ 29000) and 20 ml aqueous solution of H2PtCl6·6H2O (6.0 mM) in a 500 ml flask for 3 h. Then by means of rotary evaporator, the methanol was removed. Furthermore, the NPs in the residual solution were precipitated by acetone and subsequently collected by centrifugation at 6000 rpm


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for 2 min, and excess free PVP of the sample was removed by chloroform and hexane. Finally, the Pt NPs was dispersed in methanol with the concentration of 1.3 mM. Procedure for encapsulating MNPs in MOFs: Pt@ZIF-67. Typically, 5 ml methanol solution of 2-methylimidazole (32.84 mg, 80 mM), 5 ml methanol solution of Co(NO3)2·6H2O (58.21 mg, 40 mM) were mixed together and then the mixture was kept reacting for 8 min, followed by the adding of an extra 0.3 ml Pt NPs (~3 nm) solution of desired concentration. And the reaction mixture was kept at room temperature for 24 h without stirring. Subsequently, the precipitates were collected by centrifugation, washed with methanol for more than three times, and then vacuum-dried overnight. The sample was named as Pt@ZIF-67. Synthesis of porous Co3O4 and porous Pt@Co3O4. The porous Co3O4 was prepared via pyrolysis of the as-obtained ZIF-67. The pyrolysis temperature was based on the TGA results and set at 350 °C. In a typical process, 250 mg ZIF-67 was placed in a tube furnace which was flushed by a mixed gas (2 vol. % O2 balanced with helium) with a speed of 30 ml min-1 to remove air before heated. Then the furnace was heated to the target temperature of 350 °C under air flow at a rate of 5 °C min-1 for 1 h to pyrolyze the surface of MOFs. Finally, the product was taken out. The porous Pt@Co3O4 composites were synthesized by this process in which heating and cooling rates are essential for the uniform particle size distribution. The product was characterized by powder XRD, FESEM, EDX, and TEM. Catalytic CO oxidation. The catalytic activity of all samples obtained for CO oxidation was measured in a fixed-bed flow reactor with 50 mg catalysts and with a gas flow consisting of CO (1.5 ml min-1), He (60 ml min-1) and O2 (30 ml min-1). The reaction temperature increased by 10 °C (Pt@Co3O4 and Co3O4) and 20 °C (Pt@ZIF-67, ZIF-67 and Co3O4 (commercial)) at every


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turn and was kept stable for 10 min. Then the composition of the gathered tail gas was analyzed and the conversion rate of CO was further calculated. Finally, the ingredient of the effluent gas was analyzed by a gas chromatograph (Agilent, 6890N) equipped with a Carbosieve SII column. After the test of catalytic activity, the fixed-bed was cooled down to 110 °C and kept for more than 40 h to test the catalytic stability of Pt@Co3O4 composites. RESULTS AND DISCUSSION The MOFs can be easily transformed to metal oxide composites with the morphology and partial porosity of MOFs. The as-prepared ZIF-67 and Pt@ZIF-67 composites as precursors were properly calcinated to obtain the nanoporous metal oxides particles, generating nanoporous Co3O4 and Pt@Co3O4 composites, respectively (Scheme 1). The porous Pt@Co3O4 composites with well-defined structure can be obtained via a simple solid-state thermolysis of the Co-based MOF strategy. To the best of our knowledge, the direct heat treatment of MOFs is a controllable and simple method to prepare various metal oxides by a one-step process calcination of MOFs. Through this simple strategy, we can successfully fabricate the Pt@Co3O4 composites as a novel catalyst for CO oxidation reaction. The morphology, crystal structure and porosity of the as-obtained MOFs (ZIF-67 and Pt@ZIF-67) and MOFs based derivatives (Co3O4 and Pt@Co3O4) were characterized by using a field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), the powder X-ray diffraction patterns (PXRD) and nitrogen adsorption-desorption isotherm. Meanwhile, the thermal stability of as-obtained ZIF-67 was investigated by thermogravimetric analysis (TGA) (Figure S2, Supporting Information), which demonstrating that a weight loss was found when the temperature reached up to ∼350 °C. As shown in Figure 1,


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the as-prepared ZIF-67 and Pt@ZIF-67 composites showed a well-defined rhombic dodecahedral morphology. Meanwhile, the as-prepared ZIF-67 and Pt@ZIF-67 composites shared the uniform particle sizes, with the average sizes of 500 nm and 2 µm, respectively. The Pt NPs (~3 nm) were successfully encapsulated into ZIF-67 and the Pt NPs dispersed well in the matrixes of ZIF-67 (Figure 1d). The MOFs based derivatives, porous Co3O4 and Pt@Co3O4 composites, were easily prepared through carbonization process under air at 350 °C for 1 h (Figure 2). Moreover, they well maintained the original morphology of as-obtained ZIF-67 and Pt@ZIF-67 composites under the suitable pyrolysis condition. There mainly appeared six characteristic peaks of simulated ZIF-67 at 7.42854, 10.46932, 12.81624, 14.7958, 16.53048 and 18.1223 degree, respectively (Figure S1g). Compared to that of the simulated ZIF-67, the XRD pattern of the asobtained ZIF-67 and Pt@ZIF-67 composites found no crucial loss of crystallinity. And there was no obvious Pt NPs characteristic peak in XRD spectrum of Pt@ZIF-67 composites, probably due to the low concentration of Pt NPs encapsulated into ZIF-67 (Figure S1, Supporting Information). In the meantime, the XRD spectrum of the MOFs-derived Co3O4 and Pt@Co3O4 composites were corresponding to that of the simulated Co3O4 (Figure 3b), indicating that MOFs have been successfully transformed to the metal oxide (Co3O4). In this study, the porous structures of MOFs and MOFs-derived metal oxides were analyzed through the curves of nitrogen adsorption-desorption isotherm (Figure 3a). It demonstrated that the as-obtained ZIF-67 and Pt@ZIF-67 composites nanostructure exhibited the performances of microporous materials (type-I behavior). Specifically, in N2 uptake under relatively low pressure, ZIF-67 and Pt@ZIF67 composites displayed the microporous structure at the initial increasing stage. And the Brunauer-Emmett-Teller (BET) surface areas of ZIF-67 and Pt@ZIF-67 were 1300 m2 g-1 and 1369 m² g-1, respectively. Different from ZIF-67 and Pt@ZIF-67, Co3O4 and Pt@Co3O4


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composites are regarded as mesoporous materials (type IV behavior), which can be confirmed by the existence of hysteresis loop in N2 adsorption–desorption isotherms. Observably, in comparison with that of MOFs, the BET surface area of MOFs-derived metal oxides decreased to some extent (Co3O4 is 67.8718 m² g-1 and Pt@Co3O4 is 72.1566 m² g-1). And the average pore radius of Pt@Co3O4 and Co3O4 are 10.1459 nm and 10.1687 nm, respectively. The MOFs based derivatives, Co3O4 and Pt@Co3O4 composites as catalysts were chosen to study the activity and stability in the reaction of CO oxidation reaction. 50 mg different kinds of catalysts (the as-obtained ZIF-67, Pt@ZIF-67 composites, Co3O4, Pt@Co3O4 composites and commercial Co3O4) were respectively put into a fixed-bed flow reactor, and the flow gas consisted of CO (1.5 ml min−1), He (60 ml min−1) and O2 (30 ml min−1). Compared with other kinds of catalysts, the Pt@Co3O4 composites exhibited the remarkable catalytic performance in the reaction of CO oxidation. CO could be completely converted to CO2 at 110 °C by use of Pt@Co3O4 composites as catalysts. By comparison, the MOF-derived Co3O4 as catalyst showed a lower catalytic activity and 100% CO conversion rate required the temperature to be as high as 145 °C (Figure 4a). Importantly, we can draw the conclusion that the Co3O4 catalyst derived from ZIF-67 exhibited much better performance than the commercial Co3O4, and neither the asprepared ZIF-67 nor the Pt@ZIF-67 composites as catalysts had catalytic activity for CO oxidation reaction at 110 °C. Indeed, when the temperature reached up to 180 °C, the asprepared ZIF-67 and the Pt@ZIF-67 composites achieved the CO conversion rate of only 7.34 % and 16.54%, respectively. Taken together, these results clearly demonstrated that during the CO oxidation reaction, there was almost no catalytic activity of the as-obtained ZIF-67 and the Pt@ZIF-67 composites catalysts even at higher temperature. Nevertheless, the MOFs based derivative, Pt@Co3O4 composites, showed a higher catalytic activity in the CO oxidation


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reaction, probably due to the fact that the particular hollow and porous structures provided more active surface area and the Pt NPs were encapsulated in Co3O4 without any aggregation. Additionally, the Pt@Co3O4 composites still maintained the framework structure after the CO oxidation reaction. When the reactions were kept at 110 °C for more than 40 h after the activity test (Figure 4b), the conversion rate of the Pt@Co3O4 composites decreased slightly but the rate still kept nearly 100%, indicating that the porous Pt@Co3O4 composites had a high thermal stability for the CO oxidation reaction (Figure S3-S5, Supporting Information). And ICP-AES indicated that the amount of Pt for Pt@Co3O4 after the CO oxidation is 1.0 wt% and almost equal to that of the Pt@Co3O4 before the reaction. CONCLUSIONS In summary, MOFs based derivatives, Co3O4 and Pt@Co3O4 composites were successfully fabricated through solid-state thermolysis of as-prepared ZIF-67 and Pt@ZIF-67 composites under suitable calcination temperature and air atmosphere. The Pt@Co3O4 composites still kept the morphology of ZIF-67 and owned the hollow structure, enabling the functional derivative to exhibit the high catalytic activity in the reaction of CO oxidation. The Pt@Co3O4 composites can effectively facilitate the reaction of CO oxidation typically at a lower temperature (100% conversion rate at 110°C) than that for the as-obtained ZIF-67 (nearly bears no catalytic activity even at 180 °C) and MOF-derived Co3O4 (100% conversion rate at 145 °C). Moreover, the Pt@Co3O4 was very stable under 110 °C for more than 40 h and the conversion rate in the CO oxidation reaction decreased slightly after reaction. Interestingly, compared with the contrastive MOF-derived Co3O4, the Pt@Co3O4 composites catalyst displayed an excellent performance for CO oxidation reaction due to the encapsulation of Pt NPs in the metal oxide. Notably, this


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strategy can be extended to the preparation of other functional MOFs based derivatives with the special hollow structure, which in a sense can further expand the applications of MOFs. Supporting Information. Experimental details, more SEM images, TEM images XRD spectra and TGA curve. AUTHOR INFORMATION Corresponding Author Prof. Fengwei Huo, Email: [email protected] Author Contributions Wenlan Ji and Zhiling Xu designed experiments, performed, analyzed the results, and drafted the manuscript. Pengfei Liu and Suoying Zhang helped design the experiments. Hongfeng Li, Linjie Li and Tao Zhang were responsible for part of the TEM and SEM characterization. Professor Xiaohua Lu supplied the facilities for catalysis experiments. Professor Weina Zhang and Professor Jiansheng Wu helped to revise the manuscript. Professor Fengwei Huo supervised the project, helped design the experiments, and revised the manuscript. All authors contributed to the analysis of the manuscript. Notes The authors declare no competing financial interest. ACKNOWLEDGMENT The project was supported by the Jiangsu Provincial Founds for Distinguished Young Scholars (BK20140044), the National Science Foundation for Distinguished Young Scholars (21625401),


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the National Natural Science Foundation (21574065, 21604040, 21604038), the Jiangsu Specially-Appointed Professor, the Jiangsu Provincial Founds for Natural Science Foundation (BK20160975, BK20160981, BK20160993), the Program for Outstanding Young Scholars from the Organization Department of the CPC Central Committee, and the National Key Basic Research Program of China (2015CB932200).

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Wu, R.; Qian, X.; Rui, X.; Liu, H.; Yadian, B.; Zhou, K.; Wei, J.; Yan, Q.; Feng, X.-Q.;

Long, Y.; Wang, L.; Huang, Y. Zeolitic Imidazolate Framework 67-Derived High Symmetric Porous Co3O4 Hollow Dodecahedra with Highly Enhanced Lithium Storage Capability. Small 2014, 10, 1932-1938. 30.

Teranishi, T.; Hosoe, M.; Tanaka, T.; Miyake, M. Size Control of Monodispersed Pt

Nanoparticles and their 2D Organization by Electrophoretic Deposition. J. Phys. Chem. B. 1999, 103, 3818-3827.

Scheme 1. Schematic illustration of the preparation for the functional MOFs based derivative.


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Figure 1. The morphology and structure of MOFs. The SEM images of (a) ZIF-67; (b) Pt@ZIF67; the TEM images of (c) ZIF-67; (d) Pt@ZIF-67 and the circles represent Pt NPs.


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Figure 2. The morphology and structure of MOFs based derivatives. The SEM images of (a) Co3O4; (b) Pt@Co3O4; the TEM images of (c) Co3O4; (d) Pt@Co3O4; (e)-(g) EDX mapping images of Pt@Co3O4.


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Figure 3. (a) Nitrogen adsorption-desorption isotherm of Pt@ZIF-67, ZIF-67, Pt@Co3O4 and Co3O4 catalysts. (b) The powder X-ray diffraction patterns of Pt@Co3O4 and Co3O4 catalysts.

Figure 4. (a) CO conversion of different catalysts (the CO oxidation reactions were tested by the increase of 10 °C at every turn when Pt@Co3O4 and Co3O4 were used as catalysts. But for ZIF67, Pt@ZIF-67 and Co3O4 (commercial), the reactions were tested by the increase of 20 °C at every turn), and (b) catalytic stability of Pt@Co3O4 catalyst in CO oxidation reaction.


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