Tunable rhenium–ceria–zirconia catalysts for efficient deoxydehydration of C₆ polyols: lattice engineering enables high muconate yield

Abstract

Sustainable routes to adipic acid from biomass-derived C₆ polyols typically rely on a two-step deoxydehydration (DODH)–hydrogenation sequence, of which the DODH step remains the primary barrier to industrial adoption. Here, we report a tunable rhenium catalyst supported on ceria–zirconia mixed oxides (Re/Ce_xZr_1−xO₂) engineered through precise control of metal-support interactions. Thermal diffusion of Zr⁴⁺ into CeO₂ nanorods induces lattice contraction and elevates the Ce³⁺ fraction, substantially enhancing the reducibility of surface rhenium species and accelerating the rate-determining step in Re-catalyzed DODH. Remarkably, up to 70 at% Zr can be incorporated without structural degradation, providing an unprecedented combination of oxygen mobility and rhenium redox synergy. The optimized Re/Ce_0.3Zr_0.7O₂ catalyst delivers trans, trans-muconate in 93% yield from galactarate using n-butanol, which functions simultaneously as solvent and green reductant.

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New concepts

This work introduces a lattice-engineering strategy that unlocks the full catalytic potential of rhenium-based deoxydehydration (DODH) by precisely tuning the reducibility of ceria–zirconia mixed oxides at the nanoscale. Rather than modifying the active metal itself, we demonstrate that controlled Zr⁴⁺ diffusion into CeO₂ nanorods contracts the oxide lattice and elevates the Ce³⁺ population, creating an oxygen-vacancy-rich support that dramatically accelerates the turnover-limiting Re⁶⁺ → Re⁴⁺ reduction step during catalysis. Distinct from prior DODH studies that focus on rhenium speciation, ligand design, or reaction conditions, this work establishes the support lattice as an active kinetic regulator. Importantly, we reveal that excessive Zr incorporation disrupts solid-solution behavior, inducing lattice relaxation and phase segregation that reverses catalytic benefits—highlighting a previously unrecognized composition-structure-reactivity boundary in Ce–Zr oxides. The key insight is that oxide lattice compressibility and redox flexibility can be rationally programmed through nanoscale compositional tuning, enabling dynamic regeneration of active metal sites under reaction conditions. This principle provides a broadly applicable framework for designing next-generation heterogeneous catalysts in biomass upgrading and redox-driven transformations, where catalyst regeneration—not intrinsic activity—limits performance.

Introduction

Adipic acid (hexanedioic acid) is a key monomer for nylon-66, polyesters, and plasticizers, with a global annual demand exceeding 3.5 million tons.^1–4 Conventional production from ketone-alcohol (KA) oil via nitric acid oxidation generates substantial nitrous oxide (N₂O), a long-lived greenhouse gas, highlighting the urgent need for greener synthetic routes.^5–7 In this context, catalytic valorization of lignocellulosic carbohydrates has emerged as a promising alternative, enabling the conversion of C₆ sugars and polyols into 1,6-dicarboxylic acids that can be transformed into adipic acid through a sequential deoxydehydration (DODH)–hydrogenation pathway.^8–12

The DODH reaction, which removes vicinal hydroxyl groups to afford olefin intermediates, is typically mediated by rhenium-based catalysts (Fig. 1(a)).^13–19 In heterogeneous systems, the redox and structural properties of the oxide support strongly influence rhenium speciation^20–23 and govern the rate-determining reduction of Re⁶⁺ to Re⁴⁺, a key step that regenerates active sites for catalytic turnover.²¹ CeO₂ is a versatile oxide support owing to its intrinsic Ce³⁺/Ce⁴⁺ redox flexibility.^24–26 However, this redox flexibility alone is insufficient to efficiently drive polyol DODH or to sustain effective Re redox cycling during catalysis, thereby necessitating additional metal promoters, such as Au nanoparticles.^27–29

Fig. 1 (a) Rhenium-catalyzed deoxydehydration (DODH) of a biomass–derived C₆ polyol. (b) Schematic illustration of Re species supported on CeO₂ and lattice–modified CeO₂.

Here, we present a lattice-engineered Re/Ce_xZr_1−xO₂ nanorod catalyst that achieves highly efficient DODH of biomass-derived C₆ polyols. Controlled thermal diffusion of smaller Zr⁴⁺ ions into the CeO₂ lattice produced mixed-oxide supports containing up to 70 at% Zr—a substantially high level—while preserving the structure. This extensive Zr incorporation induced lattice contraction and enriched Ce³⁺ sites, thereby enhancing the reducibility of supported Re species (Fig. 1(b)).^30–32 Among the prepared catalysts, Re/Ce_0.3Zr_0.7O₂ exhibited outstanding activity in the DODH of galactarate using n-butanol as both solvent and green reductant, delivering trans, trans-muconate in 93% yield as a single product. Overall, this work demonstrates how nanoscale lattice engineering and oxygen-vacancy modulation in mixed oxides can strengthen metal-support redox synergy, advance rhenium-catalyzed DODH, and contribute sustainable adipic-acid production from renewable carbon sources.

Results and discussion

Zirconium-doped ceria nanorods (Ce_xZr_1−xO₂) were prepared by thermally incorporating zirconium into preformed CeO₂ nanorods to systematically probe the effects of Zr incorporation within a uniform nanorod framework (Fig. 2(a)). Pristine CeO₂ nanorods were synthesized via the hydrothermal treatment of Ce(NO₃)₃·6H₂O in 6 M NaOH aqueous solution,³³ followed by post-synthetic Zr diffusion. Defined amounts of ZrO(NO₃)₂·H₂O were added to 400 mg of CeO₂ nanorods, treated at 180 °C for 10 h, and subsequently calcined at 600 °C for 6 h in air. The resulting mixed oxides were designated Ce_0.5Zr_0.5O₂, Ce_0.3Zr_0.7O₂, and Ce_0.2Zr_0.8O₂ based on their atomic ratios determined by X-ray photoelectron spectroscopy (XPS) (Fig. 2(b)). As higher amounts of Zr⁴⁺ were incorporated, the Ce³⁺ (902.3, 898.9, 883.9, 880.6 eV) concentration and oxygen-vacancy (O_V, 531 eV) density both increased, and the nanorod surfaces became rougher, while the overall rod-like morphology maintained intact (Fig. 2(c)–(d) and Fig. S1).

Fig. 2 Preparation for ceria–zirconia nanorods (Ce_xZr_1−xO₂). (a) Synthetic scheme for Ce_xZr_1−xO₂ nanorods. (b) XPS-determined Ce/Zr atomic ratios. (c) Ce 3d and (d) O 1s XPS spectra of the mixed oxides.

The incorporation of Zr⁴⁺, which has a smaller ionic radius (0.84 Å) than Ce⁴⁺ (0.97 Å), induces local lattice strain and thereby lowers the oxygen-vacancy formation energy.^34–37 As the Zr⁴⁺ content increases, both the oxygen-vacancy density and Ce³⁺ concentration increase, accompanied by a positive shift of the O 1s XPS peak. This shift originates from the combined effects of the higher electronegativity of Zr⁴⁺ and the partial reduction of ceria (Fig. 2(c) and (d)). The enhanced oxygen-vacancy concentration in Ce_0.3Zr_0.7O₂, compared to bare CeO₂, was further confirmed by electron paramagnetic resonance (EPR) spectroscopy (Fig. S2).^38,39 Consequently, incorporation of the more electronegative Zr⁴⁺ generates more reducible nanorod supports for Re catalysis, which is also reflected by the systematic shift of the O 1s peak toward higher binding energy (Fig. 2(d)).^40–43

Rhenium oxide was subsequently impregnated onto pristine CeO₂ and each mixed-oxide support to produce the Re/Ce_xZr_1−xO₂ catalysts (Fig. 3(a)). The Re loadings, determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES), were 4.8–5.2 wt% across all samples (Table S1). Transmission electron microscopy (TEM) revealed that their overall rod-like morphology was well preserved after Re impregnation (Fig. 3(b)–(e)). XPS analysis of the Re/Ce_xZr_1−xO₂ catalysts revealed that the trend of increasing Ce³⁺ concentration and oxygen-vacancy formation with higher Zr⁴⁺ content is retained after Re impregnation (Fig. 3(f)–(g)). Notably, compared with their corresponding Ce_xZr_1−xO₂ supports, the Re/Ce_xZr_1−xO₂ catalysts exhibit further enhanced Ce³⁺ populations and oxygen-vacancy densities. Although charge transfer from Re to the oxide support would typically shift the O 1s XPS peak toward lower binding energy,⁴⁴ the O 1s XPS of Re/Ce_xZr_1−xO₂ instead show a positive binding energy shift. This behavior can be explained by electron back-donation from the highly reduced Ce_xZr_1−xO₂ supports,^45,46 which possess higher O_V densities, to the supported Re species. This interpretation is further supported by the progressive reduction of the Re oxidation state with increasing Zr content (Fig. S3).

Fig. 3 Synthesis and characterization of Re/Ce_xZr_1−xO₂ catalysts. (a) Synthetic scheme for preparing Re/Ce_xZr_1−xO₂. TEM images of (b) Re/CeO₂, (c) Re/Ce_0.5Zr_0.5O₂, (d) Re/Ce_0.3Zr_0.7O₂, and (e) Re/Ce_0.2Zr_0.8O₂. (f) Ce 3d and (g) O 1s XPS spectra of the catalysts.

Powder X-ray diffraction (XRD) of the Ce_xZr_1−xO₂ nanorods showed a systematic shift of the (111) reflection toward higher 2θ values with increasing Zr content, consistent with lattice contraction arising from substitution of smaller Zr⁴⁺ ions (0.84 Å) for larger Ce⁴⁺ ions (0.97 Å). Correspondingly, the lattice parameter decreased from 5.40 Å (CeO₂) to 5.36 Å (Ce_0.3Zr_0.7O₂) (Table 1 and Fig. S4), confirming Zr incorporation into the fluorite lattice. In an inconsistent trend, however, Ce_0.2Zr_0.8O₂ exhibited a slightly lower diffraction angle than Ce_0.3Zr_0.7O₂ (Table 1, entries 3 and 4). This subtle lattice expansion indicates that Ce_0.2Zr_0.8O₂ no longer maintains a single solid solution, and the phase segregation has begun to occur, as further evidenced by the STEM-EDS mapping in Fig. 5(d).⁴⁷

Table 1 Structural parameters of ceria–zirconia nanorod catalysts

Entry	Nanorod Catalysts	XRD
		2θ (°)	d111 (Å)	a (Å)
1	CeO2	28.60	3.117	5.400
2	Ce0.5Zr0.5O2	28.74	3.103	5.374
3	Ce0.3Zr0.7O2	28.82	3.094	5.359
4	Ce0.2Zr0.8O2	28.78	3.098	5.366
5	Re/CeO2	28.52	3.126	5.414
6	Re/Ce0.5Zr0.5O2	28.72	3.105	5.377
7	Re/Ce0.3Zr0.7O2	28.86	3.090	5.352
8	Re/Ce0.2Zr0.8O2	28.70	3.107	5.381

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Following rhenium impregnation, no noticeable shift in the (111) XRD reflection was detected, indicating that the Re species were dispersed on the surface rather than incorporated into the oxide lattice (Table 1, entries 5–8).³¹ As shown in Fig. 3(f), the XPS spectra of Re/Ce_xZr_1−xO₂ exhibited a further increase in the Ce³⁺ fraction compared with the parent oxides, suggesting partial reduction of Ce⁴⁺ induced by the deposited Re species. Thus, although the bulk nanorod structure remained unchanged, the surface electronic environment became more reducible—an essential characteristic for facilitating Re redox cycling during catalysis.

The DODH activity of the Re/Ce_xZr_1−xO₂ catalysts was evaluated using dibutyl galactarate 1 in n-butanol, which served as both the reaction solvent and a green reductant (Fig. 4(a)). With 5 mol% Re loading, the desired trans, trans-muconic dibutyl ester 2 was obtained in yields ranging from 14% to 93% depending on the catalyst composition (Fig. 4(b)). Re/CeO₂ afforded a low yield of 14%, while Re/Ce_0.5Zr_0.5O₂ improved the yield to 32%. Notably, Re/Ce_0.3Zr_0.7O₂ delivered the highest yield of 93%, indicating that an optimal Ce/Zr ratio maximizes redox synergy between Ce³⁺ sites and rhenium species. The enhanced performance is attributed to the elevated Ce³⁺ reduced the yield fraction, which facilitates electron transfer to rhenium and accelerates the rate-determining Re⁶⁺ → Re⁴⁺ reduction in the DODH catalytic cycle. Further Zr enrichment (Re/Ce_0.2Zr_0.8O₂) resulted in a reduced yield of product 2 (24%), despite comparable Ce³⁺ concentrations and oxygen-vacancy levels. This observation suggests that excessive Zr incorporation disrupts effective Re–Ce interfacial communication. In this case, a partially deoxydehydrated intermediate was also detected together with product 2 (Scheme S1).

Fig. 4 (a) Reaction scheme for the Re/Ce_xZr_1−xO₂-catalyzed deoxydehydration (DODH) of dibutyl galactarate 1. (b) Isolated yields of trans, trans-muconate 2 obtained over Re/Ce_xZr_1−xO₂ catalysts. Error bars represent standard errors.

Fig. 5 Comparison of Re/Ce_0.3Zr_0.7O₂ and Re/Ce_0.2Zr_0.8O₂. XPS spectra of (a) O 1s and (b) Re 4f. STEM-EDS elemental mapping of (c) Re/Ce_0.3Zr_0.7O₂ and (d) Re/Ce_0.2Zr_0.8O₂.

Re 4f XPS spectra revealed a clear correlation between catalytic activity and the proportion of Re⁶⁺ species, which increased from 34% for Re/CeO₂ to 50% for Re/Ce_0.3Zr_0.7O₂ (Fig. S3). Interestingly, Re/Ce_0.2Zr_0.8O₂ exhibited the highest Re⁶⁺ fraction (54%) yet lower activity, suggesting that excessive Zr incorporation leads to electronic isolation of Re sites rather than effective redox coupling (Fig. 5(a) and (b)). Scanning transmission electron microscopy-energy dispersive spectroscopy (STEM-EDS) line profiles supported this interpretation: whereas Re/Ce_0.3Zr_0.7O₂ displayed a uniform Ce–Zr–Re distribution, Re/Ce_0.2Zr_0.8O₂ formed a ZrO₂-riched surface layer that impeded electron transfer between Re species and Ce³⁺ sites (Fig. 5(c) and (d)).

Collectively, these results demonstrate that controlled lattice engineering via a stepwise incorporation strategy leads to the formation of a Ce_0.3Zr_0.7O₂ solid solution through Zr diffusion into ceria nanorods. The resulting Zr-induced lattice strain and enhanced Ce³⁺ population promote lattice oxygen mobility. Subsequent incorporation of Re generates highly dispersed Re species on the nanorod surface, as confirmed by EDS elemental mapping (Fig. S5), thereby constructing a structurally integrated Ce_0.3Zr_0.7O₂ interface. At this interface, oxygen-vacancy-stabilized Re species enable efficient interfacial electron transfer, maximizing the Re–Ce redox synergy. This structural tuning enhances the reducibility of the catalytic interface and boosts DODH performance, whereas excessive Zr loading leads to electronic decoupling and diminished catalytic activity.

Conclusions

In summary, zirconium incorporation into ceria nanorods was systematically tuned to enhance the performance of rhenium catalysts for the deoxydehydration (DODH) of biomass-derived C₆ polyols. Introducing up to 70 at% Zr⁴⁺ induced lattice contraction, increased the Ce³⁺ fraction, and improved the reducibility of the mixed oxide, thereby strengthening redox coupling between Re species and Ce sites. The optimized Re/Ce_0.3Zr_0.7O₂ catalyst delivered a 93% yield of trans, trans-muconate from galactarate under mild conditions using n-butanol as a green reductant. These findings establish a clear relationship between lattice strain, oxygen-vacancy formation, and catalytic performance in Re-catalyzed DODH. Appropriate Zr incorporation effectively tunes the Ce–Zr lattice to promote electron transfer between Re and Ce³⁺ centers, enhancing redox efficiency. This lattice-engineering strategy provides a practical framework for designing mixed-oxide supports with tailored redox properties to enable selective and sustainable biomass conversion.

Author contributions

G. H. Y., H. S., and J. P. carried out the organic reactions. H. C., H. S., G. Y., and A. J. synthesized the catalysts. The catalysts and experimental data were analysed by H. C., G. Y., Y. S., and D. Y. The manuscript was written by Y. S. and D. Y., who also designed the project. All authors have approved the final version of the manuscript.

Conflicts of interest

There are no conflicts to declare.

Data availability

All data is available in the main text or in the supplementary information (SI). The supplementary information contains detailed experimental procedures along with additional figures and tables related to catalyst characterization. See DOI: https://doi.org/10.1039/d5nh00816f.

Acknowledgements

This work was financially supported by the Yang-Young Foundation, Samyang Corporation of Korea, the National Research Foundation of Korea (RS-2024-00398065) (D. Y.) and the Research Center Program of the IBS (IBS-R006-D1) in Korea (D. Y).

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Footnote

† These authors contributed equally to this work.

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