Efficient solar-simulated-driven valorization of non-edible oils for biodiesel production via interfacial localized photothermal catalysis

doi:10.1016/S1872-2067(26)65087-5

Abstract

Abstract:

Harnessing solar energy as a power source for sustainable fuel production from biomass waste presents an effective solution to energy and environmental challenges. However, efficient utilization of low-energy near-infrared (NIR) light (representing ~50% of solar irradiance) continues a critical bottleneck especially for non-edible oils valorization. Here, we report a cellulose-derived sulfonated hydrochar (PC-SO₃H-1) utilizing the full solar spectrum for highly efficient biodiesel production, achieving a remarkable biodiesel yield of 98.29% within only 30 min, which far exceeds the theoretical limit. Favorable NIR absorption of narrow bandgap PC-SO₃H-1 combined with substrate adsorption capacity enhanced by -SO₃H functionalization overcomes thermodynamic equilibrium limitations. The optimized charge transfer dynamics accelerate the interfacial localized photothermal effect, driving the esterification reaction forward while minimizing heat loss and significantly enhancing the utilization of NIR photons. Density functional theory calculations demonstrate the formation of crucial intermediate ester carbonyl groups (C=O), with PC-SO₃H-1 effectively reducing the activation energy barrier associated with the rate-limiting process. This sustainable noble metal-free photothermal catalytic system of high-efficiency overcomes the reliance of traditional photocatalysis on high-energy photons, offering novel insights into the full spectrum solar-driven production of green and renewable biofuels.

Key words: Photothermal catalysis, Biodiesel, Near-infrared light, Liquid biomass, Esterification reaction

Heng Zhou, Longfei Hong, Yan Zhang, Yuyue Zhou, Sheng Chu, Huiyan Zhang, Hui Li, Tianyi Ma, Heng Zhang. Efficient solar-simulated-driven valorization of non-edible oils for biodiesel production via interfacial localized photothermal catalysis[J]. Chinese Journal of Catalysis, 2026, 87: 156-169.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65087-5

https://www.cjcatal.com/EN/Y2026/V87/I8/156

Figures/Tables 6

Scheme 1. (a) Current methods for biodiesel production. (b) Traditional noble metal-based photothermal materials. (c) Elaboration of the key highlights in this work.

Fig. 1. Synthesis and characterization of target catalysts. (a) Schematic representation of the preparation for PC-SO3H-1. (b) HOMO-LUMO gap of OA. Simulated adsorption of OA at -OH (c), -COOH (d), and -SO3H (e). SEM images of PC-1 (f), PC-SO3H (g), and PC-SO3H-1 (h) (inset: the corresponding particle size distribution). (i) Element mapping images of PC-SO3H-1. XRD patterns (j) and FT-IR spectra (k) of cellulose, PC, PCC, PC-1, PC-SO3H, and PC-SO3H-1. N2 adsorption-desorption isotherms (l) and Raman spectra (m) of PC-1, PC-SO3H, and PC-SO3H-1.

Fig. 2. Optical properties and bonding structure. (a) ESP image of SGQD model. (b) UV-Vis DRS of cellulose, PC, PCC, PC-1, PC-SO3H, and PC-SO3H-1. XPS valence band spectra (c) and energy band structures (d) of PC-1, PC-SO3H, and PC-SO3H-1. (e) Spatial distribution of LUMO and HOMO orbits of GQD, CGQD, and SGQD. High-resolution C 1s (f), O 1s (g), and S 2p (h) XPS spectra of PC-1, PC-SO3H, and PC-SO3H-1. The XAS spectra of C K-edge (i) and O K-edge (j) of PC-1, PC-SO3H, and PC-SO3H-1. (k) The XAS spectra of S L-edge of PC-SO3H and PC-SO3H-1.

Fig. 3. Photoelectrochemical characterization and adsorb ability. EIS Nyquist plots (a) and transient photocurrent response curves (b) of cellulose, PC, PCC, PC-1, PC-SO3H, and PC-SO3H-1. (c) PL spectra of PC-1, PC-SO3H, and PC-SO3H-1. (d) OA adsorption properties of PC-1, PC-SO3H, and PC-SO3H-1. (e) The Eads of each adsorption site on SGQD for OA and MeOH. Model fitting of adsorption kinetics (f), internal diffusion modeling (g), and adsorption isotherm (h) of OA adsorption on PC-SO3H-1.

Fig. 4. Evaluation of photothermal catalytic performance. Infrared thermography pictures (a) and temperature change curves (b) under full spectrum irradiation of PC-1, PC-SO3H, and PC-SO3H-1. (c) COMSOL simulation results under full spectrum irradiation. (d) The variation of biodiesel yield with time under full spectrum irradiation of PC-1, PC-SO3H, and PC-SO3H-1. Infrared thermography pictures (e) and temperature elevating curves (f) under irradiation of UV-vis, NIR, and full spectrum. (g) The variation of biodiesel yield with time under different conditions (dark + heating (70 °C), UV-vis, NIR, and full spectrum) by PC-SO3H-1. (h) Arrhenius plots of PC-SO3H-1 under different light conditions. (i) Comparison of biodiesel yield performance under different light conditions (with/without cooling). (j) Reusability and 10-fold magnification experiment. (k) Comparison of catalytic activity and reaction time of different catalysts.

Fig. 5. Mechanism insights of photothermal catalytic esterification reaction. (a) Effect of scavenging agents on biodiesel yield. EPR signals depicting TEMPO-h+ (b) and DMPO-CH3O• (c) in PC-SO3H-1 photothermal catalytic esterification of OA. (d,e) In situ DRIFTS spectra during photothermal catalytic OA esterification with PC-SO3H-1 under UV-vis light irradiation, NIR light irradiation, and full spectrum. (f) Calculated reaction Gibbs free energy diagram of OA esterification (Catalyst-free, PC-1, PC-SO3H, and PC-SO3H-1). (g) Schematic diagram of catalytic mechanism enhanced by the photothermal effect.

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