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. 2020 Jun 25;5(26):16183–16188. doi: 10.1021/acsomega.0c01759

In Situ One-Step Synthesis of Platinum Nanoparticles Supported on Metal–Organic Frameworks as an Effective and Stable Catalyst for Selective Hydrogenation of 5-Hydroxymethylfurfural

Kaixuan Wang †,‡, Weiliang Zhao ‡, Qingxiao Zhang ‡, Hexing Li †,‡,*, Fang Zhang ‡,*
PMCID: PMC7346239  PMID: 32656440

Abstract

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A facile in situ one-step route for the preparation of platinum nanoparticles supported on metal–organic frameworks (MOFs) without adding stabilizing agents was developed. The obtained 10% Pt@MOF-T3 material possessed a large surface area and high crystallinity. Meanwhile, uniform and well-dispersed platinum nanoparticles were formed inside the cavities of MOFs, which could be attributed to the efficient complexation and stabilization effect derived from the dipyridyl groups. The as-synthesized 10% Pt@MOF-T3 sample showed high activity and selectivity in the hydrogenation of 5-hydroxymethylfurfural (HMF). This excellent catalytic performance could be attributed to the synergistic effects of well-dispersed platinum nanoparticles and electron donation offered by MOFs. Meanwhile, the presence of bipyridine ligands in the MOF framework avoided the irreversible adsorption of the hydrocarbon compounds, leading to the enhanced catalytic efficiency. Besides, it was easily recycled and reused at least five times, showing good recyclability.

Introduction

Metal nanoparticle (MNP) catalysts are one of the most important classes of heterogeneous catalysts. Recently, the metal nanoparticle catalysts have been extensively applied in the production of chemicals, clean fuels, and pharmaceuticals, pollutant treatment, utilization of solar energy, and hydrogen production.1−3 Due to their high specific surface energy, the effective control of their size, dispersion, and stability is a key to enhance the catalytic activity and selectivity of MNPs.4,5 Unfortunately, their increased surface energy with decreased particle size inevitably causes the MNPs to be thermodynamically unstable and prone to aggregation, thereby leading to their inferior performances during catalytic reactions.6 A promising approach to solve this problem is the use of support materials to disperse and fix the MNPs.7 However, to obtain uniform and well-dispersed MNPs, compared to encapsulation in an oxide or carbon layer support, their confinement inside porous materials, for example, porous silica, zeolites, polymers and porous carbons, which could provide more accessible active sites due to the large exposed surface, is paramount for subsequent catalysis.8−10 Furthermore, porous materials offer inherent conditions for spatial confinement for efficiently limiting the aggregation and growth of MNPs, and their pores serve as a transfer path for the reaction substrates/products. This has been rarely considered to date, and the post-synthetic impregnation step for MNP incorporation is the most widely applied protocol for the preparation of supported MNP catalysts.

Recently, metal–organic frameworks (MOFs) as a class of very promising porous materials assembled from metal ions/clusters and organic ligands have been investigated extensively, owing to their ordered crystalline structure, controllable porosity, high surface area, and tunable pore size as compared to other porous materials.11−14 These unique features of MOFs have been utilized in many applications, including gas storage, separations, chemical sensing, drug delivery, and heterogeneous catalysis.15−19 Over the past decades, most of the research efforts have been aimed at preparing new MOF structures and studying their application in gas storage and separation. And recently, the application of MNPs loaded inside the porous matrices of MOFs has also attracted enormous scientific interest because the rational combination of MNPs and MOFs effectively synergizes their respective strengths and offsets their drawbacks for enhanced catalysis.20−22 Accordingly, the well-defined MOF structures enable clear surrounding environments for MNPs, which are preferable for understanding catalysis.

Diverse synthetic methods for MOF-embedded MNPs have been developed. To date, the preparation of MNP/MOF composites has been carried via three approaches, The first approach is building MOF structures around preformed MNPs, also known as “bottle-around-ship”.23−25 However, this approach often requires certain surfactants and capping agents on the surface of the presynthesized MNPs to anchor the heterogeneous growth of MOFs and avoid homogeneous MOF nucleation. In addition, it is difficult to completely wash away the additional binder, and this might be unfavorable for the effective contact of the reaction substrate with the active sites, resulting in decreased catalytic properties of MNPs. The second and the most widely utilized strategy is the use of MOFs as template materials that provides a confined space for MNPs. In this approach, the incorporation of MNPs onto MOFs can be based on different techniques, including solution impregnation, vapor deposition, solid grinding, and microwave irradiation.26−29 But, these synthetic techniques generally comprise two steps. Firstly, a metal precursor is introduced into the MOF porous network, followed by various reduction methods for the metal precursors to generate MNPs. For instance, Kaskel and co-workers incorporated Pd NPs into an MOF-5 framework via the solution impregnation approach.30 Xu’s group using the double solvents method successfully immobilized Pt nanoparticles inside an MIL-101 matrix.31 Fischer’s group first reported MNPs stabilized with MOFs using the CVD method.32 Haruta’s group first demonstrated that the solid grinding method can be effective in loading Au NPs into various types of MOFs, including Al-MIL-53, MOF-5, CPL-1, and HKUST-1.33 However, using this approach remains a significant challenge to confine all of the MNPs inside the pores. The third approach is a one-step synthesis of MNPs@MOFs. Compared to previous stepwise approaches, the one-step synthesis method is convenient and effective, as it only needs mixing of the metal precursor and starting materials for the MOFs, followed by a self-assembly process to afford MNP@MOF composites. Furthermore, this methodology can effectively avoid the diffusion resistance between the external and internal MOF surfaces and is conducive to the uniform distribution of NMPs on the MOF materials. But, until now, the utilization of the one-step synthesis strategy for the preparation of MOF-embedded MNPs has been very rare. Recently, Li and co-workers developed a one-step strategy to encapsulate small Pd NPs inside UIO-67 networks.34 In this synthetic system, the bipyridine ligand serves as the anchor site for the metal to limit the aggregation of Pd particles during the MOF self-assembly process, but it still needs additional reductants. Improving this strategy one step further, this group used the DMF solvent and H2 as mild reductants for metal precursors to incorporate tiny Pt MNPs into MOF matrices.35 Recently, Lamberti and co-workers have developed a series of zirconium metal–organic framework UiO-67 functionalized with platinum bipyridine coordination complexes.36 However, to our knowledge, both use bipyridine ligands as the anchor sites and one-step synthetic strategies without the introduction of additional reductants to prepare Pt nanoparticles inside MOFs matrices have not been reported so far. Herein, for the first time, we developed a facile capping and reducing agent-free strategy for uniformly distributing platinum nanoparticles inside MOF matrices by a convenient in situ one-step protocol that involved a ligand design prior to MOF assembly. Interestingly, in contrast to previous reports, the bipyridine ligand on the MOF framework effectively overcomes the problem of the mismatch between the reduction rate of metal nanoparticles and the MOF assembly speed to obtain uniformly dispersed platinum nanoparticles. Notably, this heterogeneous Pt catalyst exhibited excellent catalytic activity and selectivity toward hydrogenation of 5-hydroxymethylfurfural (HMF). Meanwhile, it could be easily reused and recycled for at least five times without the remarkable loss of the activity, showing a good potential in the future industrial applications.

Results and Discussion

The fabrication procedure of the Pt@MOF material is depicted in Scheme 1. First, dichlorooxozirconium octahydrate (ZrOCl2·8H2O), biphenyldicarboxylate (bpdc), and the Pt(II)-bipyridine complex (Pt(II)(Ph)2-bpydc) were used as the starting materials, and benzoic acid was used as the MOF-formation modulator for one-step assembly of 10% Pt@MOFs-T3 under N,N-dimethylformamide (DMF) as the solvent without any additional protective agents and reductants.

Scheme 1. Illustration of In Situ One-Step synthesis of 10% Pt@MOFs-T3.

Scheme 1

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We first investigated the effect of the amount of the Pt(II) complex on the encapsulation process. Considering the large steric hindrance of metal complexes, biphenyldicarboxylic acid (bpdc) was introduced into the synthesis system as a bridging ligand to assemble the MOF network. As revealed by powder X-ray diffraction (XRD) patterns (Figure S1), with the increasing amount of the Pt(II) complex, the characteristic diffraction peak intensity of Pt@MOF samples decreases significantly. This result means that the large steric hindrance of metal complexes destroys the integrity of the MOF network, resulting in a loss of crystallinity. And fortunately, the characteristic XRD peaks of all of the above 10% Pt@MOF-T3 samples matched well with those of the parent UiO-67. Furthermore, no identifiable peaks associated with Pt NPs were observed, possibly as a result of the low Pt content (0.97 wt %) and the small particle size. The N2 adsorption–desorption isotherm of the 10% Pt@MOF-T3 sample (Figure S2 and Table S1) was similar and consistent with that of the UiO-67, exhibited a typical type I isotherm, suggesting a microporous structure. The large specific surface area and uniform pore size were 1165 m2/g and 2.16 nm, respectively. Then, we further investigated the effect of the synthesis temperature on the MOF self-assembly process. As shown in Figure 1, as the reaction temperature increases, the diffraction peak is significantly enhanced. This means that the crystallinity of the Pt@MOF material increases significantly. Accordingly, the specific surface area of the Pt@MOF material also increases (Figure 2). However, the changes in synthesis temperature did not affect the encapsulation and dispersion of Pt by MOF, and the steep rise of the adsorption curve in the high-pressure region is due to the large pores formed by the accumulation of 10% Pt@MOF-T2 particles.37 As shown in Figure 3b–d, the Pt nanoparticles in all samples maintained a uniform distribution. But, the particle size of MOFs increases significantly with the increase of the synthesis temperature, indicating that the temperature accelerates the nucleation rate of MOFs, thus promoting the encapsulation of nanoparticles and effectively avoiding the aggregation and growth of nanoparticles. Interestingly, Pt nanoparticles were not found at the edge of the MOFs. We further analyzed the X-ray photoelectron spectroscopy (XPS) spectrum of the 10% Pt@MOF-T3 sample with argon ion etch technology; as shown in Figure S3, the peaks of the Pt(0) species from 70.7 and 74.2 eV are preserved after sputtering at 10 and 20 nm, respectively. These results clearly demonstrated the successful incorporation of metallic Pt(0) species in the MOF cavities.

Figure 1.

Figure 1

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Powder X-ray diffraction patterns of 10% Pt@MOF-T1, 10% Pt@MOF-T2, and10% Pt@MOF-T3 samples. (Their synthesis temperatures were 80, 95, and 120 °C, respectively).

Figure 2.

Figure 2

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N2 adsorption–desorption isotherms of 10% Pt@MOF-T1, 10% Pt@MOF-T2, and 10% Pt@MOF-T3 samples.

Figure 3.

Figure 3

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Transmission electron microscopy (TEM) images of (a) UIO-67, (b) 10% Pt@MOF-T1, (c) 10% Pt@MOF-T2, (d) 10% Pt@MOF-T3, (e) 10% Pt(II)@MOF-D, and (f) 10% Pt/UIO-67 samples.

To better understand the formation process of the Pt NPs in DMF, we chose dimethyl sulfoxide (DMSO) which has no reducibility, as the reaction solvent to synthesize the Pt@MOF material (noted as 10% Pt(II)@MOFs-D). As illustrated in Figure 3e, powder X-ray diffraction (XRD) patterns and N2 adsorption–desorption isotherm characterization data (Figures S4 and S5) show that the two samples have similar structures. Interestingly, the TEM images show that no nanoparticles are formed in the MOF networks synthesized using DMSO as the solvent. We further use XPS spectra (Figure 4) to analyze the electronic states of these samples. The Pt 4f XPS spectrum of the 10% Pt@MOF-T3 sample showed that the Pt 4f7/2 and 4f5/2 binding energies were 71.7 and 75.1 eV, respectively, which indicated that Pt species were present in the zero-valent state. However, the Pt 4f7/2 and 4f5/2 binding energies in the 10% Pt(II)@MOFs-D and precursor Pt(II)(Ph)2-bpydc compound were 72.4 and 75.7 eV, respectively, and corresponded to Pt species in the divalent state. These results clearly demonstrated the successful incorporation of metallic Pt(0) species in the MOF cavities.

Figure 4.

Figure 4

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XPS spectra of 10% Pt@MOF-T3, 10% Pt(II)@MOF-D, and Pt(II)(Ph)2-bpydc samples.

2,5-DMF is considered a potential renewable fuel due to its interesting properties, such as a high-octane number, high energy, and density, among others. Recently, the selective catalytic hydrogenation of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (2,5-DMF) by using Pt catalysts has attracted much attention.38 To investigate the utility of our novel Pt@MOF catalysts, we carried out the liquid–phase selective hydrogenation of HMF to 2,5-DMF with the Pt@MOF materials under H2 pressure (Scheme 2). We first focused on the preparation of 2,5-DMF from HMF. As shown in Table 1, the control test revealed that the blank experiment without the Pt-based catalyst did not give any products. Next, a series of Pt@MOF catalysts with different synthesis temperatures were tested (entries 2–4) and the results showed that 10% Pt@MOFs-T3 displayed good conversion (99.5%) and excellent yield (86.1%) after 8.0 h. The inferior catalytic performances of entries 2–3 were probably attributed to the poor MOF framework and lower specific surface areas and fewer exposed active sites, which increased the mass transfer resistance. Furthermore, the effect of the reaction parameters, including the reaction temperature, time, pressure, and solvents, in the 10% Pt@MOF-T3-catalyzed model reaction was investigated (Table 1, entries 6–9, Tables S3 and S4). Interestingly, as shown in Tables S3 and S4, 2,5-di(hydroxymethyl)furan (BHMF), 5-methylfurfural (MFF), and 5-methyl-2-furanmethanol (MFM) were detected owing to the simultaneous hydrogenation reactions of the hydroxyl and aldehyde groups. As shown in Table S4, under the low pressures (1.0 and 2.0 MPa), a total of 26.6 and 22.0% of the intermediates were detected (containing BHMF, MFF, and MFM), respectively. However, a high H2 pressure (4.0 MPa) will lead to a reduced selectivity of 2,5-DMF due to the excessive hydrogenation of HMF. To our satisfaction, 10% Pt@MOFs-T3 achieved the excellent conversion (99.6%) and yield (96.1%) by using 1-butanol as the solvent at 140 °C for 8.0 h under 3.0 MPa H2 pressure conditions. To confirm the excellent catalytic performance of 10% Pt@MOFs-T3, 5.0% Pt@MOFs-T3 was chosen as the control catalyst. The powder X-ray diffraction (XRD) pattern and N2 adsorption–desorption isotherm (Figures S1 and S2) showed that 5.0% Pt@MOFs-T3 had higher crystallinity and a larger specific surface area (1115 m2/g) in comparison to 10% Pt@MOFs-T3. The ICP test found that it had a low Pt content of 0.47 wt %. Furthermore, as shown in Table 1, the 5.0% Pt@MOF-T3 sample gave 66.1% conversion and 43.5% yield. The inferior catalytic performance of the 5.0% Pt@MOF-T3 sample was probably attributed to the reduced chance of contact between the active sites and the reactants. We also tested the catalytic activity of 10% Pt/UiO-67 prepared by the post-modification method. The powder X-ray diffraction (XRD) patterns and N2 adsorption–desorption isotherm characterization data (Figures S6 and S7) show that the 10% Pt/UiO-67 sample prepared by the postmodification method has lower crystallinity and a smaller specific surface area of 609 m2/g. Furthermore, as shown in Table 1, entry 11, the 10% Pt/UiO-67 sample provided 33.1% conversion and 15.1% yield. The inferior catalytic performances of 10% Pt/UiO-67 are probably attributed to the fact that the Pt-metal particles dispersed on the MOF’s outer surface are easily agglomerated and deactivated, which is consistent with the characterization results of TEM (Figure 3f). Meanwhile, the inferior catalytic efficiency of 10% Pt(II)@MOFs-D (Table 1, entry 12) was probably assigned to the Pt species in the divalent state.

Scheme 2. Possible Reaction Pathway of 5-Hydroxymethylfurfural (HMF) Hydrogenation.

Scheme 2

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Table 1. Catalytic Performances of Different Catalysts in the Synthesis of 2,5-Dimethylfuran (2,5-DMF) from 5-Hydroxymethylfurfural (HMF)a.

entry catalyst temperature (°C) solvent conversion (%) yield (%)
1 blank 120 1-butanol    
2 10% Pt@MOFs-T1 120 1-butanol 43.7 25.6
3 10% Pt@MOFs-T2 120 1-butanol 78.5 65.3
4 10% Pt@MOFs-T3 120 1-butanol 99.5 86.1
5 5.0% Pt@MOFs-T3 120 1-butanol 66.1 43.5
6 10% Pt@MOFs-T3 120 toluene 46.1 16.8
7 10% Pt@MOFs-T3 120 1-pentanol 87.0 80.7
8 10% Pt@MOFs-T3 130 1-butanol 99.1 86.5
9 10% Pt@MOFs-T3 140 1-butanol 99.6 96.1
10 10% Pt(II)@MOFs-D 140 1-butanol 15.2 6.1
11 10% Pt/UIO-67 140 1-butanol 33.1 15.1
12 10% Pt@MOFs-T3 after five reuses 140 1-butanol 99.5 87.7
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a

Reaction conditions: 2.0 mmol of HMF, 0.02 mmol of Pt, 12.0 mL of the organic solvent, 3.0 MPa H2, 1000 rpm, and 8.0 h.

The reusability of 10% Pt@MOFs-T3 was demonstrated from the recycling experiments of selective hydrogenation of HMF to 2,5-DMF. Figure 5 shows no appreciable reduction of the reactivity even after five runs. The powder X-ray diffraction (PXRD) patterns of the reused catalyst suggested that the MOF structure was completely preserved after the reactions (Figure S8). Furthermore, the N2 adsorption–desorption isotherm (Figure S9) shows that the reused material still has a high specific surface area and uniform pore size of 986 m2/g and 2.3 nm, respectively. However, the TEM image (Figure S10) indicates that the recycled catalyst has partial particle aggregation, which is probably responsible for the slightly decreased reactivity of the recycled 10% Pt@MOF-T3 catalyst after five repetitions.

Figure 5.

Figure 5

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Recycling test of the 10% Pt@MOF-T3 catalyst.

Conclusions

In summary, we have developed a facile capping and reducing agent-free strategy for uniformly distributed platinum nanoparticles inside MOF matrices by a convenient in situ one-step protocol that involved a ligand design prior to MOF assembly. This heterogeneous Pt catalyst exhibited excellent catalytic activity and selectivity toward hydrogenation of HMF. Importantly, it can be reused five times without remarkable loss of catalytic activity.

Experimental Section

Sample Preparation

Synthesis of 10% Pt@MOFs-T3

In a typical preparation, 0.60 mmol of zirconium oxychloride octahydrate, 0.06 mmol of Pt(II)(Ph)2-bpydc, 0.54 mmol of 4,4′-biphthalic acid, and 2.0 g of benzoic acid were dissolved in DMF (20 mL) in a 50 mL Schlenk tube. The mixture was sonicated to dissolve it completely and then heated at 120 °C for 24 h. The solid was isolated by centrifugation and washed with DMF and methanol. Subsequently, the sample was dried under vacuum at 100 °C overnight to remove the solvents.

Synthesis of UIO-67

The synthesis method of UIO-67 was the same as mentioned above except that Pt(II)(Ph)2-bpydc was replaced by 2,2-bipyride-5,5-dicarboxylic acid (H2bpdc).

Synthesis of 10% Pt/UIO-67

In a typical preparation, 100 mg of UIO-67 was dispersed into anhydrous ether, and then, a freshly prepared anhydrous ether solution of [Pt(Ph)2(Et2S)]2 (0.1 M, 1.0 mL) was rapidly added to the mixture under vigorous stirring for 8.0 h; next, a freshly prepared solution of NaBH4 (0.5 M, 5.0 mL) was slowly dropped into the mixture, continuously stirring for 2.0 h. Finally, the powder was washed thoroughly with methanol and dried under vacuum at 100 °C for 2.0 h to obtain the 10% Pt/UIO-67.

Characterization

The platinum loading was measured with an inductively coupled plasma optical emission spectrometer (Varian VISTA-MPX). Powder X-ray diffraction (PXRD) data was obtained on a Rigaku D/maxr B diffractometer using Cu Kα radiation. N2 adsorption–desorption isotherms were analyzed at 77 K with a Micromeritics TriStar II 3020 analyzer. The platinum electronic states were analyzed using an X-ray photoelectron spectroscope (XPS, Perkin-Elmer PHI 5000C ESCA using Al Kα as the excitation source with a base pressure of 10–9 Torr). All of the binding energy values were calibrated using C 1s = 284.6 eV as a reference. TEM images were obtained on a JEOL JEM-2011 transmission electron microscope.

Activity Test

In a typical run, 2.0 mmol of HMF, 0.02 mmol of 10% Pt@MOFs-T3 catalyst (based on ICP of Pt), 12.0 mL of 1-butanol were added into a 25 mL autoclave. The mixture was stirred at 120 °C for 8.0 h under 3.0 MPa H2 pressure. After that, the reaction mixture was filtered, and then, the organic phase was analyzed by an Agilent 1070 series gas chromatograph with an Agilent HP-5 nonpolar chromatographic column. The conversion of HMF and the yield of 2,5-DMF were determined using n-decane as the internal standard sample. All of the data were repeated at least twice, and the data error was guaranteed within ±5%.

In order to determine the stability of the 10% Pt@MOFs-T3 catalyst, it was allowed to settle down after each run of the reactions and then the clear supernatant liquid was decanted slowly. The residual solid catalyst was reused with a fresh charge of HMF and 1-butanol for subsequent recycle experiments under the same reaction conditions.

Acknowledgments

This work was supported by the NSFC (21677098), Shanghai Government (19SG42, 19520710700 and 18230742500), and the Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning (TP2016034).

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.0c01759.

  • Texture properties of different MOF samples; XRD and N2 adsorption–desorption isotherm information; activity of the 10% Pt@MOF-T3 catalyst at different times and pressures; XPS spectra of 10% Pt@MOFs-T3; XRD and TEM of the reused catalyst (PDF)

The authors declare no competing financial interest.

Supplementary Material

ao0c01759_si_001.pdf (443.1KB, pdf)

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