Metal/H+ sites modulation in the decatungstate+Pd/C catalytic system for photocatalytic generation of furfuryl ethyl ether

doi:10.1016/S1872-2067(25)64746-2

Abstract

Abstract:

Furfuryl ethyl ether (FEE) is considered as one of the most important candidates for biofuels due to its high-octane number. However, it is still challenging to produce FEE via the biomass-based route under mild conditions. Here, we developed a photoinduced catalytic transfer hydrogenation (CTH) process for the efficient production of FEE through the reduction etherification of furfural (FF) using Na₄W₁₀O₃₂ (NaDT), Pd/C, and ethanol as the hydrogen atom transfer (HAT) catalyst, hydrogenation catalyst, and the H donor, respectively. Notably, the introduction of brominated benzene (PhBr) as an additive significantly promoted the yield of FEE to 92.7%. A series of experiments and characterization results indicated that the attachment and detachment of Br atoms on Pd/C catalyst surface effectively regulate the balance between H⁺ sites and Pd sites in the NaDT+Pd/C catalytic system. The balance facilitates the preferential acetalization of FF catalyzed by H⁺ sites, followed by hydrogenation to efficiently produce FEE catalyzed by Pd sites. This photoinduced CTH process exhibits good stability and recyclability as well as universality for the transformation of various organic substrates under mild conditions.

Key words: Furfuryl ether, Decatungstate, Photocatalysis, Catalytic transfer hydrogenation, Biomass valorization

Li Zheng, Zeng Ying, Dong Yuanyuan, Lv Hongjin, Yang Guo-Yu. Metal/H⁺ sites modulation in the decatungstate+Pd/C catalytic system for photocatalytic generation of furfuryl ethyl ether[J]. Chinese Journal of Catalysis, 2025, 75: 137-146.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64746-2

https://www.cjcatal.com/EN/Y2025/V75/I8/137

Figures/Tables 9

Scheme 1. The transformation of FF into FEE via hydrogenation and etherification pathway (a), reductive etherification pathway (b), and photoinduced CTH pathway (c).

Table 1 Screening of reaction conditions for this photoinduced CTH system a.

Entry	Catalyst	FF Conv. (%)	FA yield (%)	FEE yield (%)	2-MF yield (%)	DOF yield (%)	H_abs^b (μmol)	S_FF^c (%)	S_H2^d (%)
1	NaDT + Pd/C	99.9	85.3	2.4	9.7	2.5	869.2	49.2	50.8
2	NaDT + Pt/C	64.2	2.3	0.3	0.6	61.4	724	2.1	97.9
3	NaDT + Ru/C	66.8	0	0	0	66.8	112	0	100
4^e	NaDT + Pd/C	0	0	0	0	0	—	—	—
5	Na₂WO₄ + Pd/C	3.4	0	0	0	0	—	—	—
6	Pd/C	5.4	0	0	0	0	—	—	—
7	NaDT	10.6	0	0	0	10.5	—	—	—

Fig. 1. (a) The effects of the NaDT amount on the photocatalytic activities. (b) The plots of the SFF and the transfer amount of H species (Htransfer) as function of the NaDT amount.

Fig. 2. (a) The common paths for the transformation of furan aldehydes into furan ethers. (b) The influences of the aryl halide additives on the photocatalytic activities. (c) The optimization of PhBr dosage. (d) Recycling experiments of this photoinduced CTH system.

Fig. 3. (a) The kinetic behaviors of the transformation of FF without PhBr additive. (b) The total abstracted amount and the utilization efficiency of H species without PhBr additive. (c) The proposed transformation routes of FF via photoinduced CTH method. (d) The kinetic behaviors of the transformation of FF with PhBr additive. (e) The total abstracted amount and the utilization efficiency of H species with PhBr additive. Habs here is the total amount of H species abstracted from ethanol, calculated by the sum of the H species using for H2 evolution, the hydrogenation of FF, and the hydrogenolysis of PhBr.

Table 2 Screening of Br sources for the conversion of FF into FEE via photoinduced CTH method a.

Entry	Br source	FF Conv. (%)	FEE yield (%)	Br chemical environment	Conversion of Br sources^b (%)
1		99.9	92.7	C(sp²)-Br	100
2		99.8	69.0	C(sp³)-Br (benzyl Br)	65.9
3		94.8	5.0	C(sp³)-Br	21.8
4		99.9	3.4	C(sp³)-Br	17.9
5	HBr	99.9	54.5	—	—
6	NaBr	99.8	3.0	—	—
7^c	—	99.8	33.2	—	—

Fig. 4. (a) The dynamic behavior of PhBr during photocatalysis. (b) The high-resolution Pd 3d XPS spectra of the isolated Pd/C after reaction for 0.5 h. (c) TEM image and line scan profiles of the isolated Pd/C after reaction for 0.5 h. (d) The amount of CO adsorbed on the isolated Pd/C as the prolonging time.

Scheme 2. Proposed reaction mechanism of the reduction etherification of FF via photoinduced CTH method.

Table 3 The photocatalytic activities of other substrates catalyzed by TBADT.

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