FDCA Yield Research Articles

Facilitating the electrooxidation of 5-hydroxymethylfurfural on nickel hydroxide through deintercalation

The electrocatalytic of 5-hydroxymethylfurfural oxidation reaction (HMFOR) is an alternative route for the green production of valuable oxygenated chemicals. Nickel hydroxides, which consist of hydroxide layers and interlayer charge-balancing anions, are a type of promising catalysts for HMFOR. Progresses have been made on elucidating the correlation between the hydroxide layer and HMFOR performance, while the effect of intercalated anions on the activity remains unclear. Herein, two self-supported nickel hydroxide catalysts (i.e., pristine Ni(OH)2/CP-F and deintercalated Ni(OH)2/CP-A) are employed for revealing the relationship between anion-deintercalation and HMFOR activity. Physical characterizations demonstrate that the deintercalation phenomenon can alter the d-band center and increase the electron density of the Ni site. This endows the deintercalated Ni(OH)2/CP-A with improved electrochemical properties (conversion = 99.99 %; FDCA yield > 99 %; FE > 99 %), enhanced adsorption strength for HMF, and increased intrinsic activity, compared to the pristine Ni(OH)2/CP-F. This work not only reports an excellent HMFOR electrocatalyst, but also manifests the crucial effect of deintercalation on the electrochemical oxidation performance of Ni(OH)2.

Co-N-C catalyst with single atom active sites for base-free aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid under mild conditions

The production of 2,5-furandicarboxylic acid (FDCA), a promising biodegradable alternative to fossil-based terephthalic acid (PTA), from biomass-derived 5-hydroxymethylfurfural (HMF) is of significant importance. A major challenge is to develop an effective non-precious metal catalyst system that does not require a homogeneous base. In this study, we present a noble-metal-free Co-N-C catalyst, derived from the pyrolysis of cobalt-phenanthroline complexes on a carbon support. This catalyst demonstrates exceptional performance, achieving a FDCA yield of 99.9 % and maintaining reusability for up to five catalytic cycles in the base-free oxidation of HMF to FDCA under mild conditions. Through controlled experiments and comprehensive characterizations, we propose that the active sites in the Co-N-C catalyst are Co single atoms bonded to nitrogen within graphitic sheets. This approach provides valuable insights into the exact nature of the active sites in such noble-metal-free M-N-C catalysts designed for biomass conversion

Surface reconstructed Ni0.95Pt0.05/Si photoelectrodes for bias-free hydrogen evolution coupled with 5-hydroxymethylfurfural oxidation.

Coupling hydrogen evolution reaction (HER) with biomass valorization using a photoelectrochemical (PEC) system presents a promising approach for effectively converting solar energy to chemical energy..A crucial biomass valorization reaction is the production of value-added 2,5-furandicarboxylic acid (FDCA) via 5-Hydroxymethylfurfural (HMF) oxidation reaction (HMFOR). To achieve efficient FDCA production, we demonstrate an efficient photoanode strategy that combines metal silicidation, dopant segregation, and surface reconstruction to create a bimetallic silicide Ni0.95Pt0.05Si/n-Si photoanode. The oxide-free Ni0.95Pt0.05Si/n-Si interface prepared by the metal-silicidation process ensures efficient interfacial charge transport, while dopant segregation enhances the Schottky barrier height and photovoltage, and surface reconstruction dramatically improves the catalytic activity of the photoanode surface. The as-prepared Ni0.95Pt0.05Si/n-Si photoanode exhibited excellent PEC performance for HMFOR with high conversion of HMF (97.2%) and yield of FDCA (80.3%) under illumination. Furthermore, by integrating a surface reconstructed Ni0.95Pt0.05Si/n-Si photoanode with a Ni0.95Pt0.05Si/p-Si photocathode, a dual-photoelectrode system was constructed capable of simultaneous production of FDCA and H2, which achieves high photocurrent density of 5 mA cm-2 at zero bias under illumination. This study offers an auspicious prospect for high cost-effectiveness conversion from solar energy to industrial monomers.

Seawater-corrosion-engineered CoNi electrode for highly efficient oxidation of 5-(Hydroxymethyl)furfural

The green synthesis of 2,5-furandicarboxylic acid (FDCA), famous as a bio-based polymer monomer from the 5-hydroxymethylfurfural (HMF), offers a promising route to reduce the usage of petroleum-based polymer polyethylene terephthalate. Although the electrocatalytic preparation of FDCA rids high temperature and pressure limits, most electrocatalysts used in the HMF oxidation reaction (HMFOR) are usually fabricated in harsh conditions. Therefore, we propose a method to improve the performance of electrocatalysts in the HMFOR reaction by introducing metal salts using natural seawater as the main feedstock. The final Co-sw/NF realized a 97.4% FDCA yield and 97.3% Faraday efficiency (FE). In-situ Raman techniques identified the catalytically active species of the catalysts employed in the HMFOR process. The effect of metal salts on catalyst energy levels is discussed in detail using the ultraviolet photoelectron spectroscopy (UPS) and Tauc plot method. The adsorption performance of HMF on the catalyst was determined by calculating the d-band centers and applying open circuit potential (OCP) tests. Furthermore, we elucidate the specific mechanism in terms of electron transport pathways.

Synergistic enhancement of nickel-cobalt nano-catalysts for 5-hydroxymethylfurfural conversion via electronic structure engineering and solar intensification

The electrooxidation of 5-hydroxymethylfurfural (HMF) into vital chemical intermediates has received widespread attention. In order to achieve efficient conversion of HMF, the main focus has been on the design and development of delicate catalysts. In addition, the introduction of an external field in the reaction process can also improve the electrocatalytic efficiency. In this paper, nickel-cobalt composite oxide catalysts with controlled metal centers (Ni/Co) were synthesized by a simple “coating-calcination” method. The rational rearrangement of d-electron by Co-doping facilitated the improvement of HMF adsorption, which was further confirmed by Density Functional Theory calculations. The catalysts synthesized at the optimal Co-doping ratio could still achieve 100 % of HMF conversion, 95.65 % of 2,5-furandicarboxylic acid yield, and 92.97 % of Faraday efficiency after 25 electrochemical cycles. Crucially, we introduced solar illumination to further enhance the performance of electrooxidation HMF. The catalyst performance was further improved via local photothermal effect and additional photocurrent. Therefore, the yield of FDCA was increased by more than 27 % under 2.0 kW m−2 illuminations. An electrooxidation system constructed based on external field enhancement and catalyst design provides new insights into the efficient conversion of biomass.

One-Pot, Solvent Free Synthesis of 2,5-Furandicarboxylic Acid from Deep Eutectic Mixtures of Sugars as Mediated by Bifunctional Catalyst.

Currently one-pot conversion of sugars to 2,5-furandicarboxylic acid (FDCA) is of significant interest due to the attainability of sugars as a feedstock and the enormous potential of FDCA as a bioplastic monomer. However, it remains challenging to construct efficient catalysts for this process. In this study, Co3O4 species were anchored to a sulfonated covalent organic framework thus affording a bifunctional catalyst (Co3O4@COF-SO3H). The sulfonic acid sites dehydrate sugars to 5-hydroxymethylfurfural (HMF), which is next oxidized to FDCA as catalyzed by the Co3O4 species. Such a process was applied in the conversion of various binary and ternary deep eutectic mixtures involving choline chloride and sugars without additional solvent. The maximum FDCA yield of 84 % was obtained using glucose-fructose eutectic mixture as the substrates. Moreover, the catalyst was recyclable and stable under the applied reaction conditions. Our process eliminates the employment of organic solvents and expensive noble metal catalysts, resulting in green and economic biomass conversions.

Co@NC Chainmail Nanowires for Thermo- and Electrocatalytic Oxidation of 2,5-Bis(hydroxymethyl)furan to 2,5-Furandicarboxylic Acid.

2,5-Furandicarboxylic acid (FDCA) has emerged as an important bio-based furanic compound, which has broad application prospects in renewable energy and materials, especially in the preparation of polyethylene 2,5-furandicarboxylate (PEF). While the conventional synthesis of FDCA involves oxidation of 5-hydroxymethylfurfural (HMF) as a substitute, the thermal and chemical instability of HMF due to its aldehyde group poses challenges. A more favorable alternative is the utilization of 2,5-bis(hydroxymethyl)furan (BHMF), a non-aldehyde and more stable precursor. This study pioneeringly reports nitrogen-doped-carbon encapsulated cobalt (Co@NC) chainmail nanowires for the thermal and electrocatalytic oxidation of BHMF to FDCA. The Co@NC/NF achieved a 97.9 % conversion of BHMF with a 93.3 % yield of FDCA at 1.475 V vs. RHE, whereas thermal catalysis only obtained 14.9 % FDCA yield after 10 hours. Kinetic studies indicated that the large electrochemically active surface area and excellent kinetic parameters contribute its superior electrochemical performance. Mechanistic analysis revealed that the migration of inner electrons to the exterior modified the electronic properties of the carbon layer, thereby facilitating the oxidation of BHMF. Furthermore, the in-situ generation of high-valent cobalt species markedly accelerated the BHMF oxidation. This research underscores the potential of carbon-encapsulated metal chainmail catalysts in thermal and electrochemical biomass conversion.

Co single atoms/nanoparticles over carbon nanotubes for synergistic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid

The preparation of high-value 2,5-furandicarboxylic acid (FDCA) from biomass-based platform compound 5-hydroxymethylfurfural (HMF) is an important synthetic reaction, as the resulting FDCA holds promise to replace terephthalic acid to produce environmentally friendly polyester materials. However, due to the complex tandem nature of the oxidation of HMF to FDCA, which involves several stable intermediates, efficient conversion of HMF and achieving a high FDCA yield remain challenging. Herein, a catalyst of Co SAs/NPs@N-CNTs comprising Co single atoms (Co SAs) alongside Co nanoparticles (Co NPs) supported on carbon nanotubes (CNTs) was synthesized. Co SAs/NPs@N-CNTs exhibited outstanding catalytic activity for the selective oxidation of HMF to FDCA, achieving 100% HMF conversion and 94.2% FDCA yield. This remarkable performance was attributed to the synergistic effect between Co SAs and Co NPs. Poisoning and acid treatment experiments indicated that Co SAs served as the active sites, while Co NPs did not directly act as active sites. Instead, Co NPs merely assisted the Co SAs on the sidelines, facilitating the efficient conversion of HMF into various intermediates and promoting the further conversion of these intermediates into FDCA, thereby achieving high FDCA productivity. This strategy offers new insights for designing efficient catalysts for complex tandem reactions.

Recent advances in the synthesis of 2-Furoic Acid and 2,5-furandicarboxylic acid from furfural.

2,5-furandicarboxylic acid (FDCA) is an important organic platform compound that has been widely used in the fields of medicine, pesticides, dyes, plastics and resins due to its unique structure and properties. In recent years, with the emphasis on sustainable development and green chemistry, the synthesis of FDCA from biomass has attracted extensive attention. The catalytic conversion of furfural (FF) to FDCA has the advantages of easy availability of the raw material, environmental friendliness, economic feasibility and so on, which is an important direction for FDCA synthesis in the future. This paper mainly reviews the prepare pathways of furoic acid (FA) and FDCA using FF as a starting material, including the selective conversion of FF and FA to target products under different types of catalysts. First, the research progress in the synthesis of FA from FF was summarized, and then the advances in the catalytic conversion of FA to FDCA was reviewed. In addition, the development of efficient and green catalysts and the optimization of existing synthesis protocols are emphasized as key factors to improve the yield and purity of FDCA while reducing production costs. Finally, the opportunities and challenges were discussed.

Microwave-Assisted Conversion of 5-Hydroxymethylfurfural into 2,5-Furandicarboxylic Acid over CuCo Oxide.

A series of CuCo bimetallic catalysts were prepared via the co-precipitation method for the catalytic transformation of biomass-derived 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA). FDCA acts as a precursor for biodegradable biopolymer polyethylene furanoate production, thereby achieving a carbon-neutral approach. Out of all the synthesized catalysts, CuCo(1:1) showed remarkable catalytic activity and yielded 70.67% FDCA while achieving 100% HMF conversion in 5 minutes at 50 ℃ temperature in the presence of tert-butyl hydroperoxide as an oxidant. Synergistic effects of the catalyst, such as adsorbed oxygen, relative oxygen vacancy, lesser pore size, and pore volume, were key factors attributed to the catalyst's excellent activity. The synthesized catalyst showed good recyclability with a minimal decrease in FDCA yield up to 5 cycles. Pre and post-characterization of catalysts such as BET, TEM, FE-SEM, XRD, H2-TPR, CO2 TPD, ICP-OES, and XPS were done to correlate the catalyst's properties with its activity. In addition, the effect of reaction parameters such as stirring speed, temperature reaction time, catalyst weight, base, and oxidant was studied to achieve optimum reaction conditions. The reaction products were analyzed quantitatively and qualitatively using HPLC and HR-MS.

Bifunctional MoNi4/Nickel Foam Electro-Catalyst for Ultra-Efficient Oxidation of High-Concentration 5-Hydroxymethylfurfural and HER.

The electro-catalytic oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) provides an attractive route to produce 2, 5-furandicarboxylic acid (FDCA) as a substitute for terephthalic acid used in the plastics industry. Herein, we prepared MoNi4 alloy on nickel foam (NF) using a simple hydrothermal method followed by hydrogen reduction. Applied MoNi4/NF as the bifunctional electrodes for the electro-catalytic HMF oxidation reaction (HMFOR) and HER, 98.7 % FDCA yield and 97.3 % Faraday efficiency (FE) can be achieved even with HMF concentration as high as 200 mM. Notably, no obvious deactivation was observed after ten consecutive cycles. In-situ Raman, XANES and EXAFS results show that the nickel species of MoNi4/NF is first oxidized to Ni3+ species under the applied voltage, and after undergoing the electro-catalytic HMFOR, then reduced to Ni2-δ state (with a valence between 0 and +2) due to the electron-donating effect from Mo. MoNi4/NF with more than one electron transfer between Ni3+ and Ni2-δ during the HMFOR enables it to have excellent electro-catalytic oxidation ability toward HMFOR.

Efficient synthesis of 2,5‐furandicarboxylic acid from corncob biomass using Ru/C and sulfonated carbon catalysts in a one‐pot system

AbstractThis study proposes a novel one‐pot method to produce 2,5‐furandicarboxylic acid (FDCA), which effectively simplifies the preparation process of FDCA by directly utilizing the biomass raw material corncob and its derived carbon‐based catalysts. In this work, we first prepared two different carbon‐based catalysts from corncobs: a ruthenium‐supported catalyst (Ru/C) and a sulfonated carbon catalyst. After detailed characterization and performance testing, these two catalysts were used to catalyze the pretreated corncob mixture to produce FDCA. Under optimized conditions, even using 0.12 g of Ru/C catalyst at a microwave power of 200 W, the yield of FDCA can reach 27 mol%. In comparison, the FDCA yield of the sulfonated carbon catalyst under the same conditions was 19 mol%. This work not only demonstrates the possibility of efficient production of FDCA by utilizing biomass resources and a simplified chemical conversion process, but also highlights the importance of selecting appropriate catalysts and controlling reaction conditions in improving yields. Through this method, we can promote the development of biomass conversion technology in a more efficient and environmentally friendly direction, providing technical support for the commercial production of bio‐based chemicals.

High-Entropy Engineering in Hollow Layered Hydroxide Arrays to Boost 5-Hydroxymethylfurfural Electrooxidation by Suppressing Oxygen Evolution.

The electricity-driven 5-hydroxymethylfurfural (HMF) oxidation reaction has exhibited increasing potential to produce high-value-added 2,5-furandicarboxylic acid (FDCA). Unfortunately, the competitive oxygen evolution reaction (OER) can decrease the yield and Faradaic efficiency (FE) of FDCA under high potentials. Here, we report a general MOF-templated strategy to construct a new class of hollow high-entropy layered hydroxide array (HE-LHA) electrocatalysts including quinary, senary, and septenary phases composed of CoNiMnCuZn with Cd and Mg on carbon cloth (CC) for boosting the HMF oxidation reaction (HMFOR) by suppressing the OER. Impressively, the septenary CC@CoNiMnCuZnCdMg-LHA exhibits a low potential of 1.42 VRHE for the HMFOR but a high potential of 1.68 VRHE for the OER to achieve 100 mA cm-2, ranking it among one of the best electrocatalysts for the HMFOR. Finite element simulations show its hollow array morphology can induce a strong local electric field over all of the shell, thus favoring the electrocatalytic process. In situ electrochemical impedance spectroscopy and theoretical calculations further reveal that the Co, Ni, Cu, Zn, Mn, Cd, and Mg metals in high-entropy LHAs can accelerate the HMFOR but suppress the OER by optimizing the adsorption energy of the HMF* and OH*. This work sheds light on the rational design and construction of high-entropy nanoarchitectures for advanced electrocatalysis.

Catalytic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid using Co-N/C catalysts with stepwise base addition approach

The production of 2,5-furandicarboxylic acid (FDCA) through green reaction routes is of crucial scientific value for the production of sustainable polymers. This study explores the active centers in cobalt-nitrogen-doped carbon (Co-N/C) for FDCA production. It was established that Co-Nx synergistically along with the nitrogen-doped carbon acted as centers for 5-hydroxymethylfurfural (HMF) oxidation. This study demonstrates a sustainable method for FDCA production from HMF without using precious metals, organic solvents, and harsh basic environments. Co-N/C catalyst displayed a high FDCA yield of ∼90% in an aqueous medium under mildly basic conditions in 34 h with 100% HMF conversion. An innovative strategy of stepwise base addition has been proposed to effectively accelerate the generation reaction of FDCA. The detrimental effects of high heating rate and calcination temperature on the active centers were also thoroughly investigated. Through DFT simulations it was established that Co-Nx aided in the activation of oxygen for HMF oxidation.

Ru/MgO-catalysed selective aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid

Biomass valorisation through the selective oxidation of carbohydrate and lipid derivatives offers access to an array of platform chemicals through energy- and atom-efficient catalytic processes. Supported metal nanoparticles are promising catalysts for the aerobic selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), but typically require strong liquid base to achieve high selectivity. Here, we explore the utility of MgO as a solid base support for the Ru-catalysed aerobic oxidation of HMF, obtaining 68% FDCA yield at 160°C and 1.5 MPa of O2 using <1 mol-% metal.

Integrated electrochemical and chemical system for ampere-level production of terephthalic acid alternatives and hydrogen

2,5-Furandicarboxylic acid (FDCA), a critical polymer platform molecule that can potentially replace terephthalic acid, coupled hydrogen coproduction holds great prospects via electrolysis. However, the electrosynthesis of FDCA faces challenges in product separation from complex electrolytes and unclear electrochemical and nonelectrochemical reactions during the 5-hydroxymethylfurfural (HMF) oxidation. Herein, an electrochemical/chemical integrated system of alkaline HMF-H2O co-electrolysis is proposed, achieving distillation-free synthesis of high-purity FDCA by acidic separation/purification and hydrogen coproduction. This system achieves ampere-level current densities of 812 and 1290 mA cm−2 at potentials of 1.50 and 1.60 V, with nearly 100% FDCA yield and HMF conversion in only 6 min at 1.50 V. The electrooxidation of HMF involves a coupling of electrochemical and nonelectrochemical reactions, wherein the aldehyde group is dehydrogenated and oxidized, followed by dehydrated and oxidized of the hydroxyl group, ultimately forming FDCA. Concurrently, nonelectrochemical reactions of intermolecular electron transfer occur in HMF and aldehyde group-containing intermediates.

Ligand‐Hybridization Activates Lattice‐Hydroxyl‐Groups of NiCo(OH)x Nanowires for Efficient Electrosynthesis

AbstractElectrochemical dehydrogenation of hydroxides plays a crucial role in the formation of high‐valence metal active sites toward 5‐hydroxymethylfurfural oxidation reaction (HMFOR) to produce the value‐added chemical of 2,5‐furandicarboxylic (FDCA). Herein, we construct benzoic acid ligand‐hybridized NiCo(OH)x nanowires (BZ‐NiCo(OH)x) with ample electron‐deficient Ni/Co sites for HMFOR. The robust electron‐withdrawing capability of benzoic acid ligands in BZ‐NiCo(OH)x speeds up the electrochemical activation and dehydrogenation of lattice‐hydroxyl‐groups (M2+−O−H⇌M3+−O), boosting the formation of abundant electron‐deficient and high‐valence Ni/Co sites. DFT calculation reveals that the deintercalation proton is prone to establishing a hydrogen bridge with the carbonyl group in benzoic acid, facilitating the proton transfer. Coupled with the synergistic oxidation of Ni/Co sites on hydroxyl and aldehyde groups, BZ‐NiCo(OH)x delivers a remarkable current density of 111.20 mA cm−2 at 1.4 V for HMFOR, exceeding that of NiCo(OH)x by approximately fourfold. And the FDCA yield and Faraday efficiency are as high as 95.24 % and 95.39 %, respectively. The ligand‐hybridized strategy in this work introduces a novel perspective for designing high‐performance transition metal‐based electrocatalysts for biomass conversion.

Ligand-Hybridization Activates Lattice-Hydroxyl-Groups of NiCo(OH)x Nanowires for Efficient Electrosynthesis.

Electrochemical dehydrogenation of hydroxides plays a crucial role in the formation of high-valence metal active sites toward 5-hydroxymethylfurfural oxidation reaction (HMFOR) to produce the value-added chemical of 2,5-furandicarboxylic (FDCA). Herein, we construct benzoic acid ligand-hybridized NiCo(OH)x nanowires (BZ-NiCo(OH)x) with ample electron-deficient Ni/Co sites for HMFOR. The robust electron-withdrawing capability of benzoic acid ligands in BZ-NiCo(OH)x speeds up the electrochemical activation and dehydrogenation of lattice-hydroxyl-groups (M2+-O-H⇌M3+-O), boosting the formation of abundant electron-deficient and high-valence Ni/Co sites. DFT calculation reveals that the deintercalation proton is prone to establishing a hydrogen bridge with the carbonyl group in benzoic acid, facilitating the proton transfer. Coupled with the synergistic oxidation of Ni/Co sites on hydroxyl and aldehyde groups, BZ-NiCo(OH)x delivers a remarkable current density of 111.20 mA cm-2 at 1.4 V for HMFOR, exceeding that of NiCo(OH)x by approximately fourfold. And the FDCA yield and Faraday efficiency are as high as 95.24 % and 95.39 %, respectively. The ligand-hybridized strategy in this work introduces a novel perspective for designing high-performance transition metal-based electrocatalysts for biomass conversion.

Highly Self-Healing Co3+/Ni3+ Dual-Active Species for the Electrocatalytic Oxidation of 5-Hydroxymethylfurfural.

Electrocatalytic conversion of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is significant for the sustainable production of value-added chemicals. Active sites of catalysts could enhance the activity and selectivity of the HMF oxidation reaction (HMFOR), but the self-healing ability of active sites has been commonly ignored. In this work, Co(OH)2/Ni-MOF was successfully fabricated for efficient oxidation of HMF to FDCA under mild conditions. Electrochemical and cyclic stability experiments demonstrated the high self-healing properties of the dual active sites (Co3+/Ni3+). So, the retention rate of FDCA yield can still reach 98.5%, even after 90 days. HMFOR was further coupled with 4-nitrophenol hydrogenation, which promotes the yield and Faradaic efficiency of FDCA to about 100%. Therefore, this study explores the self-healing properties of species and provides new insights for designing efficient catalysts.

Pt nanoparticles in cooperation with Mn-P composite drive base-free selective oxidation of 5-hydroxymethylfurfural

Selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is a key approach to sustainable upgrading of furfural based biomass resources. In this work, small Pt nanoparticles (about 2.1 nm) loaded on MnPnOx composite were shown to effectively drive the base-free aerobic oxidation of HMF to FDCA in water. Regulating the P content in carrier enabled to tune HMF conversion and product distribution. The optimal Pt/MnP0.5Ox catalyst can reach 98% yield of FDCA at 110 °C under 10 bar of O2 after 24 h. It also showed the highest initial conversion rate of HMF (13 mmol molPt−1 s−1) and productivity of FDCA (4.1 mmol molPt−1 h−1) among all the Pt/MnPnOx catalysts. The carrier effect of P addition on promoting Pt oxidation catalysis was elucidated by using rigorous kinetic investigations and comprehensive characterizations. The initial conversion rate, rate constant and apparent activation energy were independently measured on oxidation of HMF and its derived intermediates. ICP-MS, XRD, TEM, H2-TPR, O2-TPD and XPS were used to acquire catalytic properties. It was demonstrated that P addition led to changes in carrier structure and metal-support interaction, which eventually promoted the formation of highly active electron-rich Pt0 sites and mobile reactive defect oxygen species. These features allowed improving the selective oxidation catalysis of supported-Pt nanoparticles for the base-free conversion of HMF to FDCA.