Highly dispersed Pd clusters/nanoparticles encapsulated in MOFs via in situ auto-reduction method for aqueous phenol hydrogenation

doi:10.1016/j.jmst.2021.08.079

Abstract

Abstract:

In this work, a novel in situ auto-reduction strategy was developed to encapsulate uniformly dispersed Pd clusters/nanoparticles in MIL-125-NH₂. It is demonstrated that the amino groups in MIL-125-NH₂ can react with formaldehyde to form novel reducing groups (-NH-CH₂OH), which can in situ auto-reduce the encapsulated Pd²⁺ ions to metallic Pd clusters/nanoparticles. As no additional reductants are required, the strategy limits the aggregation and migration of Pd clusters and the formation of large Pd nanoparticles via controlling the amount of Pd²⁺ precursor. When applied as catalysts in the hydrogenation of phenol in the aqueous phase, the obtained Pd(1.5)/MIL-125-NH-CH₂OH catalyst with highly dispersed Pd clusters/nanoparticles with the size of around 2 nm exhibited 100% of phenol conversion and 100% of cyclohexanone selectivity at 70 °C after 5 h, as well as remarkable reusability for at least five cycles due to the large MOF surface area, the highly dispersed Pd clusters/nanoparticles and their excellent stability within the MIL-125-NH-CH₂OH framework.

Key words: Pd clusters, Pd nanoparticles, MIL-125-NH₂, In situ auto-reduction, Double solvent method, Hydrogenation of phenol

Xiubing Huang, Xiaoyu Li, Wei Xia, Bin Hu, Martin Muhler, Baoxiang Peng. Highly dispersed Pd clusters/nanoparticles encapsulated in MOFs via in situ auto-reduction method for aqueous phenol hydrogenation[J]. J. Mater. Sci. Technol., 2022, 109: 167-175.

Figures/Tables 8

Scheme 1. Schematic representation of highly dispersed Pd clusters/nanoparticles inside the MIL-125-NH-CH2-OH.

Fig. 1. (a) FT-IR spectra, and (b) XRD patterns of the as-prepared samples.

Fig. 2. (a) TEM and (b) HRTEM images and (c) elemental mapping images of Pd(1.0)/MIL-125-NH-CH2OH.

Fig. 3. (a-c) TEM and EDS elemental mapping images of Pd(0.5)/MIL-125-NH-CH2OH, (d, e) Pd(1.5)/MIL-125-NH-CH2OH and (g, h) Pd(1.0)/MIL-125-NH2-PR.

Table 1. The textural properties of as-prepared samples.

Materials	S_BET(m²/g)^a	V_P(cm³/g)^b	Average pore width(nm)^c	Microporous pore width(nm)^d	Pd content(wt%)^e	Pd⁰/Pd^2+f
MIL-125-NH₂	835	0.46	2.22	0.388	-	-
MIL-125-NH-CH₂-OH	633	0.38	2.40	0.385	-	-
Pd(0.5)/MIL-125-NH-CH₂-OH	691	0.41	2.38	0.385	0.50	2.12
Pd(1.0)/MIL-125-NH-CH₂-OH	688	0.41	2.37	0.386	0.83	3.46
Pd(1.5)/MIL-125-NH-CH₂-OH	684	0.42	2.43	0.385	0.84	2.19
Pd(1.0)/MIL-125-NH₂-PR	832	0.47	2.26	0.389	0.61	1.88

Fig. 4. (a) C 1s, (b) N 1 s, and (c) Pd 3d XP spectra of as-prepared samples.

Fig. 5. Catalytic performances of as-prepared catalysts (a) as a function of reaction temperature for 4 h and (b) reaction time at 70 °C. Reaction conditions: 15 mg catalyst, 2 mL phenol aqueous solution (0.0125 mol/L), 50 psi H2 pressure, 800 rpm.

Fig. 6. Reusability tests for phenol hydrogenation after 4 h at 70 °C.

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