Dual-metal synergy unlocking ROS-free catalysis for rapid aerobic oxidation of 5-hydroxymethylfurfural at room temperature

doi:10.1016/S1872-2067(24)60151-8

Abstract

Abstract:

Clean catalytic oxidation has a broad prospect in the modern chemical engineering and energy chemistry fields. However, unexpected over-oxidation and disruptive degradation are frequently induced by excessive reactive oxygen species (ROS). Herein, we reported a new ROS-free approach to effectively drive O₂ to be activated into highly reactive surface peroxo species through enzyme-mimicking mechanism. Benefiting from the dual-metal synergy effect between Cu and Co active sites, ROS (H₂O₂ and OH^•) is generated in situ while further scavenged completely into surface peroxo species, which gives rise to very high selectivity and extremely high carbon balance. For example, the CuCo/N-C catalyst affords >99.8% conversion and 94.5% selectivity to 2,5-furanedicarboxylic acid at 25 °C for 6 h in the aerobic oxidation of biomass platform 5-hydroxymethylfurfural. Moreover, it achieved exceptional performance in the oxidation of a variety of hydroxyl compounds to organic acids with high yields (89.9%-99.5%) at a mild temperature (25-40 °C). This exploration introduces an innovative clue for emulating enzyme catalysts, thereby enriching our comprehension and advancement of biologically inspired catalytic oxidations.

Key words: Biomass, Dual metal synergy, Molecular oxygen activation, 5-Hydroxymethylfurfural, Reactive oxygen species free, Selective oxidation

Meiyun Zhang, Penghua Che, Hong Ma, Xin Liu, Shujing Zhang, Yang Luo, Jie Xu. Dual-metal synergy unlocking ROS-free catalysis for rapid aerobic oxidation of 5-hydroxymethylfurfural at room temperature[J]. Chinese Journal of Catalysis, 2024, 67: 144-156.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60151-8

https://www.cjcatal.com/EN/Y2024/V67/I12/144

Figures/Tables 10

Scheme 1. Schematic illustration dual-metal synergy of CuCo/N-C, with functions to generate ROS (a) and clearance ROS to form surface peroxo species (b), and realize the rapid oxidation of HMF to FDCA at room temperature (c).

Fig. 1. TEM images (a,b), HRTEM images (c,d), corresponding EDX maps for the overlapped Cu, Co, N, O and C (e-j), and AC HAADF-STEM images (k,l) of CuCo/N-C.

Table 1 The influence of dual-metal synergy in HMF oxidation reaction a.

Entry	Catalyst	Conversion (%)	Yield (%)			Carbon balance (%)
Entry	Catalyst	Conversion (%)	HMFCA	FFCA	FDCA	Carbon balance (%)
1^b	—	14.5	n.d.	n.d.	n.d.	0.0
2^c	—	>99.7	22.7	n.d.	n.d.	22.8
3	Cu/N-C	69.8	27.7	6.3	8.2	60.5
4	Co/N-C	>99.8	33.7	0.2	65.2	99.3
5^d	Cu/N-C+Co/N-C	>99.6	16.7	1.8	73.5	92.4
6	CuCo/N-C	>99.8	n.d.	n.d.	94.3	94.5

Fig. 2. (a) Comparison of non-precious metal catalysts in the oxidation of HMF to FDCA [27⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓-43]. (b) ROS detection at specific conditions. (c) Schematic illustration for O2 activation with CuCo/N-C and deactivation caused by cationic treatment. (d) EPR spectrum for detecting O2•- in toluene with CuCo/N-C. (e) Zeta potential of CuCo/N-C and cationic treated CuCo/N-C. (f) GC spectra for detecting H2O2 via triphenylphosphine oxidation in water in O2. (g) EPR spectrum for detecting OH• in alkaline solution in O2. Reaction conditions: 8 mg catalyst, 2 mL of H2O; 1 MPa O2, 25 °C, 30 min; For detecting O2•-, 2 mL of toluene; for detecting H2O2, 0.2 mmol triphenylphosphine; for detecting OH•, 0.023 mmol metal in catalyst, 0.8 mmol NaOH.

Fig. 3. (a) The detect process of ROS with the addition of CuCo/N-C under specific conditions. (b) MS spectrum of triphenylphosphine oxide formed by the oxidation of triphenylphosphine in water. (c) UV-Vis spectrums of KI solution in water with addition of CuCo/N-C and CuCo/N-C treated with the cationic reagent. (d) EPR spectrum of alkaline solution over CuCo/N-C. (e) the EPR spectra of the treated CuCo/N-C in different pH solution. (f) High-resolution Cu 2p XPS spectra. (g) High-resolution O 1s XPS spectra of the fresh CuCo/N-C, CuCo/N-C treated without HMF and CuCo/N-C treated with HMF. Reaction conditions: for (b), 0.023 mmol metal in catalyst, 0.2 mmol triphenylphosphine, 2 mL of H2O, 1 MPa O2, 25 °C, 30 min, for (d), 0.023 mmol metal in CuCo/N-C, 0.8 mmol NaOH, 2 mL of H2O, 25 °C, 1 MPa O2, 30 min.

Fig. 4. The intensity of DMPO-OH• adducts in the EPR spectra of the H2O2 + NaOH system with addition of different catalysts (a); the time curve of the intensity of DMPO-OH• adducts in the EPR spectra of the H2O2 + NaOH system with and without addition of CuCo/N-C (b); EPR spectrum of the DMPO-OH• adducts in the H2O2 + NaOH system (c) and in the H2O2 + NaOH system with addition of CuCo/N-C (d). Reaction conditions: in H2O2 + NaOH system, 0.8 mmol NaOH, 1.6 mL of H2O, 400 μL of 30 wt% H2O2; in isopropanol (IPA) experiment, 0.2 mmol HMF, 0.023 mmol metal in catalyst, 0.8 mmol NaOH, 2 mL of H2O, 1 MPa O2, 25 °C, 3 h.

Fig. 5. Raman spectra of Cu2O-Treated and Cu2O (a), CP-HMF and CP (b), CuO-HMF and CuO (c). (d) FTIR of Cu2O, Cu2O-Treated and CP. (e) XRD of Cu2O-Treated and Cu2O-O2. (f) CP-HMF and CuO-HMF. Scheme of transformation and cycle in Cu2O and CP (g), CuO and Cu (h). (CP represents copper peroxide nanodots synthesized according to the literature [44]).

Fig. 6. The yield in the reaction of HMF oxidation over CuCo/N-C with H2O2 adding in one time, and H2O2 adding in the speed of 0.0028 mL/min and O2 bubbling (a,b); The HPLC traces for HMF oxidation over CuCo/N-C with O2 bubbling (c); relevance of NaOH usage and catalytic performance of the CuCo/N-C (d); recycling experiments of CuCo/N-C (e). Reaction conditions: for (a), (b) and (c), 0.5 mmol HMF, 20 mg catalyst, 2 mmol NaOH, H2O, 20 mL/min O2 or 2 mL of 30 % H2O2, 25 °C; for (d), 0.2 mmol HMF, 0.023 mmol metal, 2 mL of H2O, 1 MPa O2, 25 °C, 3 h; for (e), 0.2 mmol HMF, 0.023 mmol metal in catalyst, 0.8 mmol NaOH, 2 mL of H2O, 1 MPa O2, 25 °C, 6 h.

Fig. 7. The reaction time profile of PhCH2OH oxidation over CuCo/N-C (a); The reaction time profile of PhCD2OH oxidation over CuCo/N-C (b); Linear fitting of ln(C0/Ct) against the reaction time of PhCH2OH (c); and PhCD2OH (d) over CuCo/N-C. Reaction conditions: 0.5 mmol benzyl alcohol, 0.023 mmol metal in catalyst, 2.0 mmol NaOH, 5 mL of H2O, 20 mL/min O2, 25 °C.

Table 2 Catalytic oxidation of various hydroxyl compounds to corresponding acids over the CuCo/N-C catalyst.

Entry	Temperature (°C)	Time (h)	Yield (%)
1	25	5	95.4
2	25	8	91.6
3	25	5	99.5
4	25	8	96.9
5	25	24	89.9
6	25	5	93.9
7	25	5	90.4
8	25	10	92.3
9	40	10	96.7
10	40	15	91.3

References

[1]	R. Gérardy, D. P. Debecker, J. Estager, P. Luis, J. C. M. Monbaliu, Chem. Rev., 2020, 120, 7219-7347.
[2]	C. L. Chen, M. X. Lv, H. L. Hu, L. Y. Huai, B. Zhu, S. L. Fan, Q. G. Wang, J. Zhang, Adv. Mater., 2024, DOI:10.1002/adma.202311464.
[3]	X. Y. Huang, J. T. Groves, Chem. Rev., 2018, 118, 2491-2553.
[4]	C. H. Tang, X. Qiu, Z. R. Cheng, N. Jiao, Chem. Soc. Rev., 2021, 50, 8067-8101.
[5]	R. Long, K. Mao, X. Ye, W. Yan, Y. Huang, J. Wang, Y. Fu, X. Wang, X. Wu, Y. Xie, Y. Xiong, J. Am. Chem. Soc., 2013, 135, 3200-3207.
[6]	Y. Nosaka, A. Y. Nosaka, Chem. Rev., 2017, 117, 11302-11336.
[7]	X. M. Shen, W. Q. Liu, X. J. Gao, Z. H. Lu, X. C. Wu, X. F. Gao, J. Am. Chem. Soc., 2015, 137, 15882-15891.
[8]	C. H. He, C. F. Xia, F. M. Li, J. Zhang, W. Guo, B. Y. Xia, Adv. Energy Mater., 2024, 14, 2303233.
[9]	H. Y. Gu, X. Liu, X. F. Liu, C. C. Ling, K. Wei, G. M. Zhan, Y. B. Guo, L. Z. Zhang, Nat. Commun., 2021, 12, 5422.
[10]	W. J. Yang, K. L. Sun, J. Wan, Y. A. Ma, J. Q. Liu, B. C. Zhu, L. Liu, F. Fu, Appl. Catal. B, 2023, 320, 121978.
[11]	Z. H. Xie, C. S. He, H. Y. Zhou, L. L. Li, Y. Liu, Y. Du, W. Liu, Y. Mu, B. Lai, Environ. Sci. Technol., 2022, 56, 8784-8795.
[12]	R. Mittler, S. I. Zandalinas, Y. Fichman, F. Van Breusegem, Nat. Rev. Mol. Cell Bio., 2022, 23, 663-679.
[13]	Z. F. Pei, H. L. Lei, L. Cheng, Chem. Soc. Rev., 2023, 52, 2031-2081.
[14]	X. W. Cao, C. X. Zhu, Q. Hong, X. H. Chen, K. Y. Wang, Y. F. Shen, S. Q. Liu, Y. J. Zhang, Angew. Chem. Int. Ed., 2023, e202302463.
[15]	F. W. Gu, H. C. Liu, Chin. J. Catal., 2020, 41, 1073-1080.
[16]	L. Wu, Y. Feng, F. Zeibig, M. Alam, M. Frei, Bio-Protocol, 2021, 11, e4190.
[17]	S. C. Li, Redox Biol., 2023, 64, 102789.
[18]	T. F. Liu, B. W. Xiao, F. Xiang, J. L. Tan, Z. Chen, X. R. Zhang, C. Z. Wu, Z. W. Mao, G. X. Luo, X. Y. Chen, J. Deng, Nat. Commun., 2020, 11, 2788.
[19]	Y. Chen, H. Zou, B. Yan, X. J. Wu, W. W. Cao, Y. H. Qian, L. Zheng, G. W. Yang, Adv. Sci., 2022, 9, 2103977.
[20]	Y. X. Sun, H. Ma, X. Q. Jia, J. P. Ma, Y. Luo, J. Gao, J. Xu, ChemCatChem, 2016, 8, 2907-2911.
[21]	Y. X. Sun, H. Ma, Y. J. Luo, S. Zhang, J. Gao, J. Xu, Chem. Eur. J., 2018, 24, 4653-4661.
[22]	X. Liu, Y. Luo, H. Ma, S. J. Zhang, P. H. Che, M. Y. Zhang, J. Gao, J. Xu, Angew. Chem. Int. Ed., 2021, 60, 18103-18110.
[23]	X. Liu, H. Ma, M. Y. Zhang, P. H. Che, Y. Luo, S. J. Zhang, J. Xu, ACS Catal., 2023, 13, 11104-11116.
[24]	M. Y. Zhang, H. Ma, X. Liu, S. J. Zhang, Y. Luo, J. Gao, J. Xu, ACS Appl. Mater. Interfaces, 2022, 14, 18539-18549.
[25]	Q. X. Wang, Q. Kuang, K. S. Wang, X. Wang, Z. X. Xie, RSC Adv., 2015, 5, 61421-61425.
[26]	T. Wang, H. Ma, X. Liu, Y. Luo, S. J. Zhang, Y. X. Sun, X. H. Wang, J. Gao, J. Xu, Chem. Asian J., 2019, 14, 1515-1522.
[27]	E. Hayashi, Y. Yamaguchi, K. Kamata, N. Tsunoda, Y. Kumagai, F. Oba, M. Hara, J. Am. Chem. Soc., 2019, 141, 18642-18642.
[28]	E. Hayashi, T. Komanoya, K. Kamata, M. Hara, ChemSusChem, 2017, 10, 654-658.
[29]	X. X. Dong, X. Y. Wang, H. Song, Y. Zhang, A. H. Yuan, Z. J. Guo, Q. Wang, F. Yang, ChemSusChem, 2022, 15, e202200076
[30]	H. Liu, W. L. Jia, X. Yu, X. Tang, X. H. Zeng, Y. Sun, T. Z. Lei, H. Y. Fang, T. Y. Li, L. Lin, ACS Catal., 2021, 11, 7828-7844.
[31]	X. W. Han, C. Q. Li, X. H. Liu, Q. N. Xia, Y. Q. Wang, Green Chem., 2017, 19, 996-1004.
[32]	K. Yu, Y. Q. Liu, D. Lei, Y. Z. Jiang, Y. B. Wang, Y. J. Feng, L. L. Lou, S. X. Liu, W. Z. Zhou, Catal. Sci. Technol., 2018, 8, 2299-2303.
[33]	K. T. V. Rao, J. L. Rogers, S. Souzanchi, L. Dessbesell, M. B. Ray, C. B. Xu, ChemSusChem, 2018, 11, 3323-3334.
[34]	H. Zhou, H. H. Xu, Y. Liu, Appl. Catal. B, 2019, 244, 965-973.
[35]	M. Ventura, F. Nocito, E. de Giglio, S. Cometa, A. Altomare, A. Dibenedetto, Green Chem., 2018, 20, 3921-3926.
[36]	R. Kumar, Z. Zhu, C. Z. Chen, W. F. Cai, J. W. C. Wong, J. Zhao, ChemSusChem, 2022, 15, e202201333.
[37]	H. Zhou, H. H. Xu, X. K. Wang, Y. Liu, Green Chem., 2019, 21, 2923-2927.
[38]	A. D. Cheng, M. H. Zong, G. H. Lu, N. Li, Adv. Sustainable Syst., 2021, 5, 2000297.
[39]	Y. N. Han, W. X. Qu, W. Feng, Enzyme Microb. Technol., 2021, 150, 109895.
[40]	W. P. Dijkman, D. E. Groothuis, M. W. Fraaije, Angew. Chem. Int. Ed., 2014, 53, 6515-6518.
[41]	B. Saha, D. Gupta, M. M. Abu-Omar, A. Modak, A. Bhaumik, J. Catal., 2013, 299, 316-320.
[42]	X. Y. Liu, M. Zhang, Z. H. Li, ACS Sustainable Chem. Eng., 2020, 8, 4801-4808.
[43]	S. W. Yang, C. Wu, J. H. Wang, H. D. Shen, K. Zhu, X. Zhang, Y. L. Cao, Q. Y. Zhang, H. P. Zhang, ACS Catal., 2022, 12, 971-981.
[44]	L. S. Lin, T. Huang, J. B. Song, X. Y. Ou, Z. T. Wang, H. Z. Deng, R. Tian, Y. J. Liu, J. F. Wang, Y. Liu, G. C. Yu, Z. J. Zhou, S. Wang, G. Niu, H. H. Yang, X. Y. Chen, J. Am. Chem. Soc., 2019, 141, 9937-9945.
[45]	W. Peng, X. Y. Qu, S. Shaik, B. J. Wang, Nat. Catal., 2021, 4, 266-273.
[46]	P. Wu, J. Y. Zhang, Q. Q. Chen, W. Peng, B. J. Wang, Chin. J. Catal., 2022, 43, 913-927.