Switching electronic effects of UiO-67-Pd using fluorinated ligands for catalytic oxidative arylation of bio-based furfuryl alcohol

doi:10.1016/S1872-2067(24)60207-X

Abstract

Abstract:

An efficient and novel approach is proposed for oxidative arylation of bio-based furfuryl alcohol (FA) to aryl furans (AFs), a versatile monomer of photoelectric materials, in the presence of UiO-67-Pd(F) with phenanthroline/ bipyridine, and poly-F substituted phenyl ligands as the mixture linkers. The results of control experiments and theoretical calculations reveal that the −F on the phenyl linkers efficiently tunes the electron-deficient nature of Pd through the Zr₆ clusters bridges, which favors the adsorption and activation of the furan ring. Furthermore, the conjugation of different nitrogen-containing ligands facilitates Pd coordination for the Heck-type insertion and subsequent electrophilic palladation, respectively. As a result, the oxidative arylation of FA derivatives is substantially enhanced because of these electronic and steric synergistic effects. Under the optimized conditions, 72.2% FA conversion and 74.8% mono aryl furan (MAF) selectivity are shown in the Heck-type insertion. Meanwhile, 85.3% of MAF is converted, affording 74.8% selectivity of final product (AFs) in the subsequent electrophilic palladation reaction. This process efficiency is remarkably higher than that with homogeneous catalysts. In addition, furan-benzene polymer obtained from the halogen-free synthesis catalyzed by UiO-67-Pd(F) show significantly better properties than that from conventional Suzuki coupling method. Therefore, the present work provides a new insight for useful AFs synthesis by oxidative arylation of bio-furan via rational tunning the metal center micro-environment of heterogeneous catalyst.

Key words: Bio-based furan, Catalytic oxidative arylation, UiO-67-Pd(F) catalyst, Ligand regulation, Charge separation

Dongwen Guo, Guohui Zeng, Jinxing Long, Biaolin Yin. Switching electronic effects of UiO-67-Pd using fluorinated ligands for catalytic oxidative arylation of bio-based furfuryl alcohol[J]. Chinese Journal of Catalysis, 2025, 69: 230-240.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60207-X

https://www.cjcatal.com/EN/Y2025/V69/I2/230

Figures/Tables 10

Fig. 1. Synthesis and application of aryl furan scaffolds.

Scheme 1. The synthesis of FBs-1 and FBs-2.

Fig. 2. (a) XRD patterns of UiO-67, UiO-67-Phen(F)-Pd, UiO-67-Bpy(F)-Pd, and simulated. (b) FT-IR spectra of UiO-67-Phen-Pd, UiO-67-Phen(F)-Pd, UiO-67-Bpy-Pd, UiO-67-Bpy(F)-Pd, and UiO-67. (c) SEM images of UiO-67-Phen(F)-Pd. (d,e) TEM images of UiO-67-Phen(F)-Pd. (f) The EDX spectra of UiO-67-Phen(F)-Pd. (g) SEM images of UiO-67-Phen(F)-Pd. (h,i) TEM images of UiO-67-Phen(F)-Pd. (j) The EDX spectra of UiO-67-Phen(F)-Pd. The EDX elemental mapping images of UiO-67-Phen(F)-Pd (k?q) and UiO-67-Bpy(F)-Pd (r?x).

Fig. 3. XPS spectra of UiO-67-Phen-Pd, UiO-67-Phen(F)-Pd, UiO-67-Bpy-Pd, and UiO-67-Bpy(F)-Pd: Pd 3d (a), Zr 3d (b), and F 1s (c). (d) Pd K-edge XANES spectra of UiO-67-Phen(F)-Pd and reference samples (Pd foil and PdO). (e) FT k3-weighted Pd K-edge EXAFS curves of UiO-67-Phen(F)-Pd, UiO-67-Bpy(F)-Pd and reference samples (Pd foil and PdO). (f) FT-EXAFS R space fitting curves of UiO-67-Phen(F)-Pd. (g) Pd K-edge XANES spectra of UiO-67-Bpy(F)-Pd and reference samples (Pd foil and PdO). (h) Pd k-space spectra of UiO-67-Phen(F)-Pd, UiO-67-Bpy(F)-Pd and reference samples (Pd foil and PdO). (i) FT-EXAFS R space fitting curves of UiO-67-Bpy(F)-Pd.

Fig. 4. The differential charge density of UiO-67-Phen-Pd, UiO-67-Phen(F)-Pd, UiO-67-Bpy-Pd, and UiO-67-Bpy(F)-Pd.

Fig. 5. The TDOS and PDOS for UiO-67-Phen-Pd (a), UiO-67-Phen(F)-Pd (b), UiO-67-Bpy-Pd (c), and UiO-67-Bpy(F)-Pd (d).

Table 1 Catalytic performance of the continuous oxidative arylation of furfuryl alcohol derivative (a) under various catalysts a.

Entry	Step	Catalyst	Conversion of (a)/(c) (%)	Selectivity of (b)/(d) (%)	Yield of (b)/(d) (%)	TOF ^e (h⁻¹)
1	I	None	0	0	0	—
2		UiO-67	0	0	0	—
3		UiO-67-Phen-Pd	40.3	56.8	22.9	11.9
4		UiO-67-Phen(F)-Pd	72.2	74.8	54.0	21.3
5		UiO-67-Bpy(F)-Pd	63.4	36.3	23.0	18.7
6 ^b		UiO-67-Phen(F) + Pd(TFA)₂	21.6	30.4	6.6	—
7 ^c		Pd(CH₃CN)₂Cl₂	38.1	37.5	14.3	0.4
8	II	None	0	0	0	—
9		UiO-67	0	0	0	—
10		UiO-67-Bpy-Pd	54.6	70.3	38.3	24.1
11		UiO-67-Phen(F)-Pd	77.4	41.7	32.3	34.2
12		UiO-67-Bpy(F)-Pd	85.3	86.5	73.8	37.7
13 ^b		UiO-67-Bpy(F) + Pd(TFA)₂	40.8	27.4	11.2	—
14 ^d		Pd(OAc)₂	46.6	67.9	31.6	0.7

Fig. 6. (a) The energy diagram and reaction pathways for the C?H arylation of a in the presence of UiO-67-Phen-Pd and UiO-67-Phen(F)-Pd catalysts. (b) The energy diagram and reaction pathways for the C?C bond cleavage of c in the presence of UiO-67-Bpy-Pd and UiO-67-Bpy(F)-Pd catalysts.

Fig. 7. The recyclability experiments of UiO-67-Phen(F)-Pd (a) and UiO-67-Bpy(F)-Pd (b). (c) The hot filtration tests of UiO-67-Phen(F)-Pd and UiO-67-Bpy(F)-Pd. XRD patterns (d) and XPS spectra (e) of used UiO-67-Phen(F)-Pd and UiO-67-Bpy(F)-Pd. The TEM images of fresh UiO-67-Phen(F)-Pd (f), used UiO-67-Phen(F)-Pd (g), fresh UiO-67-Bpy(F)-Pd (h), and used UiO-67-Bpy(F)-Pd (i).

Fig. 8. (a) Solid-state UV-vis absorption spectra of FBs-1 and FBs-2. Tauc plots for band gap calculation of FBs-1 (b) and FBs-2 (c). (d) Photoluminescence spectra of FBs-1 and FBs-2.

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