Microenvironment engineering of nitrogen-doped hollow carbon spheres encapsulated with Pd catalysts for highly selective hydrodeoxygenation of biomass-derived vanillin in water

doi:10.1016/S1872-2067(24)60261-5

Abstract

Abstract:

Development of efficient and stable metal catalysts for the selective aqueous phase hydrodeoxygenation (HDO) of biomass-derived oxygenates to value-added biofuels is highly desired. An innovative surface microenvironment modulation strategy was used to construct the nitrogen-doped hollow carbon sphere encapsulated with Pd (Pd@NHCS-X, X: 600-800) nanoreactors for catalytic HDO of biomass-derived vanillin in water. The specific surface microenvironments of Pd@NHCS catalysts including the electronic property of active Pd centers and the surface wettability and porous structure of NHCS supports could be well-controlled by the calcination temperature of catalysts. Intrinsic kinetic evaluations demonstrated that the Pd@NHCS-600 catalyst presented a high turnover frequency of 337.77 h^-1 and a low apparent activation energy of 18.63 kJ/mol. The excellent catalytic HDO performance was attributed to the unique surface microenvironment of Pd@NHCS catalyst based on structure-performance relationship analysis and DFT calculations. It revealed that pyridinic N species dominated the electronic property regulation of Pd sites through electronic metal-support interaction (EMSI) and produced numerous electron-rich active Pd centers, which not only intensified the dissociation and activation of H₂ molecules, but also substantially improved the activation capability of vanillin via the enhanced adsorption of -C=O group. The fine hydrophilicity and abundant porous structure promoted the uniform dispersion of catalyst and ensured the effective access of reactants to catalytic active centers in water. Additionally, the Pd@NHCS-600 catalyst exhibited excellent catalytic stability and broad substrate applicability for the selective aqueous phase HDO of various biomass-derived carbonyl compounds. The proposed surface microenvironment modulation strategy will provide a new consideration for the rational design of high- performance nitrogen-doped carbon-supported metal catalysts for catalytic biomass transformation.

Key words: Microenvironment modulation, Nitrogen-doped hollow carbon sphere, Pd-based catalyst, Electronic metal-support interaction, Hydrodeoxygenation, Vanillin

Jun Wu, Liqian Liu, Xinyue Yan, Gang Pan, Jiahao Bai, Chengbing Wang, Fuwei Li, Yong Li. Microenvironment engineering of nitrogen-doped hollow carbon spheres encapsulated with Pd catalysts for highly selective hydrodeoxygenation of biomass-derived vanillin in water[J]. Chinese Journal of Catalysis, 2025, 71: 267-284.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60261-5

https://www.cjcatal.com/EN/Y2025/V71/I4/267

Figures/Tables 15

Fig. 1. Schematic synthetic route of Pd@NHCS catalysts.

Fig. 2. XRD patterns (a), FTIR spectra (b), and Raman spectra (c) of Pd@NHCS-X (X = 600-800) catalysts. (d) TG/DTG curves of PdCl42--PDA@SiO2 precursor. N2 adsorption-desorption isotherms (e) and the corresponding pore size distribution profiles (f) of Pd@NHCS-X catalysts.

Table 1 The physicochemical properties of Pd@NHCS-X (X: 600-800) catalysts.

Catalyst	S_BET^a (m²/g)	V_pore^a (cm³/g)	D_pore^a (nm)	d_TEM^b (nm)	d_VA^c (nm)	Adsorbed hydrogen^d (μmol/g)	Pd content^e (wt%)	N content^f (at%)
Pd@NHCS-600	275.17	0.55	8.06	6.34	7.38	107.5	6.34	2.21
Pd@NHCS-700	176.32	0.46	10.37	8.37	8.93	70.0	6.63	1.40
Pd@NHCS-800	256.81	0.59	9.21	8.77	9.49	97.5	6.79	1.04

Fig. 3. SEM (a), TEM (b) and high-resolution TEM (c) images of Pd@NHCS-600 catalyst. HAADF-STEM image (d) and the corresponding elemental mapping images (e-i) of C, N, O, and Pd of Pd@NHCS-600 catalyst, respectively.

Table 2 Catalytic HDO of vanillin with different catalysts.

Entry	Catalyst	Conversion (%)	Selectivity (%)
Entry	Catalyst	Conversion (%)	VA	MMP
1	Blank	0	0	0
2	NHCS-600	0	0	0
3	Pd@NHCS-600	100	0	100
4	Pd@NHCS-700	95	10	90
5	Pd@NHCS-800	52	10	90
6	Pt@NHCS-600	10	100	0
7	Ru@NHCS-600	55	43	57
8	Co@NHCS-600	0	0	0
9	Ni@NHCS-600	0	0	0
10	Cu@NHCS-600	0	0	0
11	Pd@HCS-600	66	26	74
12	Pd@NC-600	59	47	53
13	Pd@NCS@SiO₂-600	57	44	56

Fig. 4. Effect of reaction parameters on catalytic HDO of vanillin over Pd@NHCS-600 catalyst: reaction temperature (a), catalyst dosage (b) and reaction time (c). (d) Catalyst stability study for HDO of vanillin over Pd@NHCS-600 catalyst. Reaction conditions: vanillin 0.5 mmol, catalyst 5 mg, water 5 mL, H2 0.1 MPa, 120 °C, 6 h.

Fig. 5. (a) UV-vis spectra of vanillin adsorption on Pd@NHCS-600 catalyst in water and ethanol, respectively. The adsorption profiles of vanillin (b) and vanillyl alcohol (c) on Pd@NHCS-600 catalyst in water and ethanol.

Fig. 6. Kinetic study on the selective HDO of vanillin over Pd@NHCS-X catalysts. ln(Ct/C0) vs. reaction time plots of Pd@NHCS-600 (a), Pd@NHCS-700 (b), and Pd@NHCS-800 (c) catalysts at 80-100 °C. C refers to the concentration of vanillin. The corresponding Arrhenius plots of Pd@NHCS-600 (d), Pd@NHCS-700 (e), and Pd@NHCS-800 (f) catalysts.

Fig. 7. The dynamic evolution process of water contact angles over Pd@NHCS-600 (a), Pd@NHCS-700 (b), and Pd@NHCS-800 (c) catalysts. (d) Optical photographs of Pd@NHCS-600 catalyst dispersed in water and the mixed solvent composed of water and ethyl acetate. (e) H2-TPD profiles of Pd@NHCS-X catalysts. (f) UV-vis spectra of vanillin adsorption on Pd@NHCS-X and NHCS-600 catalysts.

Fig. 8. High-resolution XPS spectra of N 1s (a), Pd 3d (b) and the contents of various N species (c) for Pd@NHCS-X catalysts. (d) Schematic diagrams of the pyridinic N and graphitic N configurations incorporated into the Pd@NHCS catalyst.

Fig. 9. (a) The binding energies of pyridinic N and graphitic N species of Pd@NHCS-X catalysts and the corresponding NHCS-X supports. (b) The binding energy of Pd0 species and the corresponding energy offsets of pyridinic-N and graphitic-N species of Pd@NHCS-X. (c) Dependences of NP/NG ratio of Pd@NHCS-X catalysts, the corresponding NHCS-X supports and their energy offsets of pyridinic-N and graphitic-N species on calcination temperature of catalyst. (d) Dependences of the binding energies of pyridinic N and graphitic N species and the binding energy of Pd0 species on Pd loading. The relationships between TOF value and Pd species content (e), N species content (f) for Pd@NHCS-X catalysts.

Fig. 10. Charge density difference and electron transfer amount of pyridinic N-doped carbon supported Pd (a) and graphitic N-doped carbon supported Pd (c), the yellow and cyan areas refer to the increase and decrease in charge density, respectively. The top view and two-dimensional charge density difference of pyridinic N-doped carbon supported Pd in (a) (b), and graphitic N-doped carbon supported Pd in (c) (d). The red and blue areas refer to the electron accumulation and depletion, respectively. (e) Calculated density of states of the structure in (a-d). (f) Adsorption energies of vanillin binding with pyridinic N and graphitic N-doped carbon supported Pd catalysts, respectively.

Fig. 11. Schematic of reaction mechanism for vanillin HDO over Pd@NHCS catalyst.

Scheme 1. The scale-up experiment of vanillin HDO over Pd@NHCS-600 catalyst. Reaction conditions: vanillin 5 mmol, catalyst 50 mg, water 10 mL.

Table 3 Catalytic HDO of various biomass-derived aldehyde and ketone derivates over Pd@NHCS-600 catalyst a.

Entry	Conversion (%)	Selectivity (%)
1	100	100
2^b	94	87
3^b	95	99
4^c	92	95
5^c	96	100
6	100	100
7^d	100	72
8^e	100	100
9^b	99	100
10^b	93	98
11	100	100
12	78	100
13	71	100

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