Electrooxidation Of Alcohols Research Articles

Hierarchical ZnCo2O4 nanorod@Ni(OH)2 nanosheet arrays on Ni foam for electrosynthesis of benzoic acid coupled with accelerating hydrogen production

Electrooxidation conversion of benzyl alcohol to value-added benzoic acid is a sustainable and environmentally method to acquire valuable chemicals and accelerate hydrogen production. However, this promising approach is limited by the expensive and less stable anode electrocatalysts and low current density at moderate cell potential. To address these challenge, herein, we develop hierarchical ZnCo2O4@Ni(OH)2 heterostructure nanoarrays on nickel foam (ZnCo2O4@Ni(OH)2/NF) for electrooxidation of benzoic alcohol coupled with hydrogen production. The as-prepared ZnCo2O4@Ni(OH)2/NF anode shows it excellent electrooxidation activity for benzyl alcohol to benzoate in 1.0 M KOH electrolyte with 0.1 M benzyl alcohol. At a constant potential of 1.62 V vs. RHE, the corresponding production rate of benzoate and H2 is 1.99 mmol cm−2 h−1 and 44.66 mL cm−2 h−1, respectively. In addition, the current density can reach 100 mA cm−2 only applying a potential of 1.48 V (vs. RHE). Above all, it exhibits high conversion of 99% and Faradaic efficiency (FE) of 96% for value-added benzoate. Moreover, it could be recycled at least eight times with stable electrocatalytic activity.

Rapid synthesis of Palladium-Platinum-Nickel ultrathin porous nanosheets with high catalytic performance for alcohol electrooxidation

Bimetallic two-dimensional (2D) nanomaterials are widely used in electrocatalysis owing to their unique physicochemical properties, while trimetallic 2D materials of porous structures with large surface area are rarely reported. In this paper, a one-pot hydrothermal synthesis of ternary ultra-thin PdPtNi nanosheets is developed. By adjusting the volume ratio of the mixed solvents, PdPtNi with porous nanosheets (PNSs) and ultrathin nanosheets (UNSs) was prepared. The growth mechanism of PNSs was investigated through a series of control experiments. Notably, thanks to the high atom utilization efficiency and fast electron transfer, the PdPtNi PNSs have remarkable activity of methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR). The mass activities of the well-tuned PdPtNi PNSs for MOR and EOR were 6.21 A mg−1 and 5.12 A mg−1, respectively, much higher than those of commercial Pt/C and Pd/C. In addition, after durability test, the PdPtNi PNSs exhibited desirable stability with the highest retained current density. Therefore, this work provides a significant guidance for designing and synthesizing a new 2D material with excellent catalytic performance toward direct fuel cells applications.

Perovskite Oxides as an Opportunity to Systematically Study the Electrooxidation of Alcohols and Polyols on Materials Based on Abundant Elements: Learning from the Experience Using Pure Metals and Metallic Oxides in Electrocatalysis

The cost-effective production of green hydrogen is one of the most important challenges for a sustainable energy transition. To decrease the cost of the production of hydrogen through electrolysis, there are several obstacles that must be overcome. For instance, more active and stable anodes made of abundant and cheap materials will contribute to lowering capital and operational expenditure. It is well known that the oxidation of water requires high overpotentials, which is the main limitation of the performance of the device. In this context, substituting the oxidation of water [oxygen evolution reaction (OER)] at the anode of electrolyzers by the oxidation of biomass-derived substances contributes to the overall process by decreasing the power input of the devices and, in some cases, by producing value-added chemicals. Herein, we revisited some of the most important fundamental aspects of the electrooxidation of alcohols and polyols on metal-based catalysts, focusing on reaction descriptors. Then, we moved to the electrooxidation of these molecules on metal oxides, revisiting some of the literature about their application in heterogeneous catalysis and for OER, to get insights about the relation of the structure of the materials and their activity. Due to the lack of fundamental knowledge about the electrooxidation of alcohols and polyols on metallic oxides and to the vast literature about the use of perovskite oxides for OER, we propose to start systematic studies using perovskite oxides for the electrooxidation of alcohols and polyols. Consequently, we presented results for LaCoO3, LaFeO3, LaMnO3, and LaNiO3 and proposed a mechanism for the electrooxidation of glycerol based on the formation and reactivity of MOH(O) species. We believe that fundamental and systematic studies on this topic would permit the establishment of reaction descriptors, speeding up the search for suitable materials for this reaction and paving the way for more cost-effective production of green hydrogen.

Promotion effects of Pr-doped CeO2·H2O to Pt catalysts toward alcohol electrooxidation reaction

Considering that the co-catalyst which are rich in oxygen vacancy and hydroxyl functional groups have an obvious role in improving the activity and durability of Pt-based electrocatalyst, a novel Pr-doped CeO2·H2O cocatalyst (PrxCey(OH)a) has been prepared through a facile one-step hydrothermal method. The substitution of Pr3+ cation for host Ce4+ cation produces oxygen vacancies due to charge compensation effects. Pt/C-Pr1Ce6(OH)a exhibits an outstanding electrochemical oxidation performance with high peak current density of 2587 mA mg−1, 4116 mA mg−1, 2158 mA mg−1 in methanol, ethylene glycol, and glycerol oxidation reaction, respectively. PrxCey(OH)a provides significant co-catalysis effects by comparing with the alcohol electrooxidation performance of Pt/C, which shows a feasible strategy for the rational design of direct alcohol fuel cells catalysts.

In Situ Reconstruction of Helical Iron Borophosphate Precatalyst toward Durable Industrial Alkaline Water Electrolysis and Selective Oxidation of Alcohols

AbstractIron‐based (pre)catalysts have attracted enormous attention for various electrooxidation reactions due to the low cost, high abundance, and multiple accessible redox states of iron. Herein, a well‐defined helical iron borophosphate (LiFeBPO) is developed as an electro(pre)catalyst for the oxygen evolution reaction (OER) and selective alcohol oxidation. When deposited on nickel foam (NF), LiFeBPO exhibits an exceptional OER performance at ambient conditions attaining a current density of 100 mA cm−2 at ≈276 mV overpotential in 1 m KOH. Notably, this anode sustains durable alkaline water electrolysis at 500 mA cm−2 for over 330 h under industrial conditions (6 m KOH and 85 °C). In –situ and ex situ investigations reveal a deep reconstruction of LiFeBPO during OER, which transforms into a 3D open porous skeleton assembled by ultrasmall, low‐crystalline α‐FeOOH nanoparticles (interfacing with NiOOH of NF). This structure contributes to exposing accessible surface active sites, as well as accelerating mass transport and bubble detachment. Moreover, this electrode also catalyzes the electrooxidation of alcohols (methanol, ethylene glycol, and glycerol) to formic acid (FA) with high selectivity and full conversion. This study provides promising solutions for designing suitable anodes for the simultaneous production of green hydrogen fuel and value–added FA from electrooxidation reactions.

Highly open one-dimensional PtNi architectures with subnanometer walls as efficient catalysts for alcohol electrooxidation

The design of efficient and sustainable platinum-based catalysts is the key to developing direct alcohol fuel cells. Here, we designed highly open, one-dimensional Pt–Ni architectures with controllable wall thickness by selectively etching Pt–Ni nanowires. Pt atoms of both the inner and outer Pt–Ni architectures can participate in the electrochemical process, dramatically increasing the number of active sites and resulting in excellent alcohol electrooxidation performance. The obtained Pt1Ni5-M architecture with an ultrathin wall of 1.18 nm and a more open structure shows the best performance. The methanol oxidation reaction and ethanol oxidation reaction mass activities of Pt1Ni5-M are 7.4 (1.93 A/mgPt) and 4.6 (0.96 A/mgPt) times higher than that of Pt/C, respectively. After 3600s chronoamperometry tests, these Pt–Ni architectures also show improved durability with limited decay. This simple strategy inspires us to create more suitable catalysts with open structures for direct alcohol fuel cells.

Controllable surface reconstruction of copper foam for electrooxidation of benzyl alcohol integrated with pure hydrogen production

AbstractElectrocatalytic water splitting that is coupled with electrocatalytic chemical oxidation is considered as one of the promising methods for efficiently obtaining hydrogen energy and fine chemicals. Herein, we focus on an electrochemical redox activation strategy to rationally manipulate the microstructure and surface valence states of copper foam (CF) and boost the corresponding performance towards electrocatalytic benzyl alcohol oxidation (EBA), accompanied by the efficient hydrogen production. Correspondingly, the Cu(II)‐dominated species are gradually formed on the CF surface with the dissolution and redeposition of copper in the suitable potential range. The new species containing Cu2O, CuO, and Cu(OH)2 during surface reconstruction process of the CF were confirmed by multiple characterization techniques. After 220‐cycled activation (CF‐220), the activated CF achieves an increase of current density for EBA in anode from 9.5 for the original CF to 29.3 mmol/cm2, while the pure hydrogen yield increases threefold than that of the original CF at 1.5 VRHE. The produced new species can endow the CF‐220 with abundant acidity sites, which can enhance the adsorption toward Lewis‐basicity benzyl alcohol, confirmed by NH3‐temperature‐programmed desorption. In situ Raman result further reveals that the as‐produced CuO, Cu(OH)2, and Cu(OH)42− are the main active species toward the EBA process.

Ultrafine PtRh-Co3O4 ternary alloy nanoparticles with enhanced electrocatalytic activity and long-term stability for alcohol electro-oxidation

To date, the development of structure-sensitive electrocatalysts is crucial, consisting of oxophilic metals and a conductive support with Pt-rich surfaces. In this study, PtRh-Co3O4 ternary alloy nanoparticles (∼2–3 nm) were uniformly distributed on carbon (PtRh-Co3O4/C) via a co-chemical reduction method. The chemical inertness and oxophilicity of Rh, along with the abundant oxygen defects of Co3O4, contributed to improving the kinetics of the methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR) in PtRh-Co3O4/C by promoting the scission of C-C and C-H bonds. PtRh-Co3O4/C displayed high intrinsic activity for both MOR (6.8 mA/cm2Pt) and EOR (3.17 mA/cm2Pt) due to the strong electronic, ligand, and bifunctional effects. Even after 7000 potential cycles, it retained 81% (MOR) and 84% (EOR) of its initial value, indicating extended stability. Compared to other Pt-based benchmark catalysts, PtRh-Co3O4/C exhibited higher CO tolerance, extended activity, and stability, making it a promising electrocatalyst with competitive performance for alcohol electro-oxidation.

Unraveling the electrophilic oxygen-mediated mechanism for alcohol electrooxidation on NiO.

Aqueous organic electrosynthesis such as nucleophile oxidation reaction (NOR) is an economical and green approach. However, its development has been hindered by the inadequate understanding of the synergy between the electrochemical and non-electrochemical steps. In this study, we unravel the NOR mechanism for the primary alcohol/vicinal diol electrooxidation on NiO. Thereinto, the electrochemical step is the generation of Ni3+-(OH)ads, and the spontaneous reaction between Ni3+-(OH)ads and nucleophiles is an electrocatalyst-induced non-electrochemical step. We identify that two electrophilic oxygen-mediated mechanisms (EOMs), EOM involving hydrogen atom transfer (HAT) and EOM involving C-C bond cleavage, play pivotal roles in the electrooxidation of primary alcohol to carboxylic acid and the electrooxidation of vicinal diol to carboxylic acid and formic acid, respectively. Based on these findings, we establish a unified NOR mechanism for alcohol electrooxidation and deepen the understanding of the synergy between the electrochemical and non-electrochemical steps during NOR, which can guide the sustainable electrochemical synthesis of organic chemicals.

Inhibitor and Activator: Dual Role of Subsurface Sulfide Enables Selective and Efficient Electro-Oxidation of Methanol to Formate on CuS@CuO Core-Shell Nanosheet Arrays.

Selective electro-oxidation of aliphatic alcohols into value-added carboxylates at lower potentials than that of the oxygen evolution reaction (OER) is an environmentally and economically desirable anode reaction for clean energy storage and conversion technologies. However, it is challenging to achieve both high selectivity and high activity of the catalysts for the electro-oxidation of alcohols, such as the methanol oxidation reaction (MOR). Herein, a monolithic CuS@CuO/copper-foam electrode for the MOR with superior catalytic activity and almost 100% selectivity for formate is reported. In the core-shell CuS@CuO nanosheet arrays, the surface CuO directly catalyzes MOR, while the subsurface sulfide not only serves as an inhibitor to attenuate the oxidative power of the surface CuO to achieve selective oxidation of methanol to formate and prevent over-oxidation of formate to CO2 but also serves as an activator to form more surface O defects as active sites and enhances the methanol adsorption and charge transfer to achieve superior catalytic activity. CuS@CuO/copper-foam electrodes can be prepared on a large scale by electro-oxidation of copper-foam at ambient conditions and can be readily utilized in clean energy technologies.

Anchoring hydroxyl intermediate on NiCo(OOH)x nanosheets to enable highly efficient electrooxidation of benzyl alcohols

AbstractSelective oxidation of alcohols to the carboxylic acid plays an important role in the production of valuable chemicals. Herein, NiCo hydroxide (NiCo(OOH)x) nanosheets with a thickness of ~4 nm were controllably fabricated in a facile way efficient for the electrooxidation of benzyl alcohol (BAL) to benzoic acid (BAD). Mechanistic studies confirmed the hydroxyl active intermediate (OH*) generated on the surface of NiCo(OOH)x nanosheets through operando electrochemical impedance spectroscopy and the electron paramagnetic resonance spectroscopy analysis during the electrooxidation process. Importantly, we discovered that the OH* was crucial to boost the selective oxidation of BAL by attacking the hydroxyl end group to achieve carboxylic acid. The early onset potential of 1.16 VRHE in the presence of BAL was below 1.23 VRHE for oxygen evolution reaction. The rotating ring‐disk electrode further revealed that the electrocatalytic BAL oxidation reaction occurred earlier in the oxygen evolution reaction. In 150 mM BAL, NiCo(OOH)x nanosheets generated a high BAD selectivity of >99% and full conversion of BAL in 3 h. The experimental and theoretical calculation revealed that the dominant pathway of BAL oxidation was the interaction between nucleophilic BAL with OH* to form BAL‐OH* directly by dehydrogenates, thereby producing BAD with high efficiency. This research sheds mechanism insights on the electrocatalytic alcohols oxidation reaction.

Electrodeposition of CoxNiy Thin Film and Its Catalytic Activity for Ethanol Electrooxidation

Platinum is often used as a catalyst in ethanol electrooxidation. Still, it has many disadvantages being expensive and its active site can be poisoned by CO. Transition metal of Co and Ni can become a catalyst in alcohol electrooxidation at a lower cost to synthesize. In this work, bimetallic CoNi were successfully prepared by electrodeposition method with different Co/Ni ratios to enhance ethanol electrooxidation. Samples of CoNi are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), and electrochemical impedance spectroscopy (EIS). XRD diffractogram confirmed the formation of CoNi. Morphology of CoNi in SEM characterization showed that CoNi with ratio 5:1 has the more dispersed particle and the greatest surface area. EDX characterization indicated that the relative weight of different Co/Ni ratios, the composition wt.% Co is 81.15% and wt.% Ni is 18.85% in CoNi 5:1, wt.% Co is 60.96% and wt.% Ni is 30.94% in CoNi 2:5, while wt.% Co is 50.19%, and wt.% Ni is 49.81% in CoNi 5:5. EIS characterization showed that CoNi with ratio of 5:1 has faster electron kinetics. Electrooxidation of ethanol used cyclic voltammetry (CV) method. The best results from the ethanol electrooxidation reaction were obtained for CoNi with a ratio of 5:1 because of the greatest surface area that showed in scanning electron microscopy and fast electron transfer kinetics compared to others ratio of CoxNiy.

Methanol and Ethanol Electrooxidation on ZrO2/NiO/rGO

Recently, transition metal oxides have been considered for various applications due to their unique properties. We present the synthesis of a three-component catalyst consisting of zirconium oxide (ZrO2), nickel oxide (NiO), and reduced graphene oxide (rGO) in the form of ZrO2/NiO/rGO by a simple one-step hydrothermal method. X-ray powder diffraction (XRD), scanning electron microscope (SEM), and bright-field transmission electron microscopy (BF-TEM) analyses were performed to accurately characterize the catalysts. Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and linear sweep voltammetry (LSV) analyses were also carried out to investigate the methanol and ethanol alcohol electrooxidation ability of the synthesized nanocatalysts. Inspired by the good potential of metal oxides in the field of catalysts, especially in fuel-cell anodes, we investigated the capability of this catalyst in the methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR). After proving the successful synthesis and examining the surface morphology of these materials, detailed electrochemical tests were performed to show the outstanding capability of this new nanocatalyst for use in the anode of alcohol fuel cells. ZrO2/NiO/rGO indicated a current density of 26.6 mA/cm2 at a peak potential of 0.52 V and 99.5% cyclic stability in the MOR and a current density of 17.3 mA/cm2 at a peak potential of 0.52 V and 98.5% cyclic stability in the EOR (at optimal concentration/scan rate 20 mV/s), representing an attractive option for use in the anode of alcoholic fuel cells.

Monodispersed ultrathin twisty PdBi alloys nanowires assemblies with tensile strain enhance C2+ alcohols electrooxidation

Direct alcohol fuel cells (DAFCs) are powered by the alcohol electro-oxidation reaction (AOR), where an electrocatalyst with an optimal electronic structure can accelerate the sluggish AOR. Interestingly, strain engineering in hetero-catalysis offers a promising route to boost their catalytic activity. Herein, we report on a class of monodispersed ultrathin twisty PdBi alloy nanowires (TNWs) assemblies with face-centered structures that drive AORs. These thin nanowire structures expose a large number of reactive sites. Strikingly, Pd6Bi1 TNWs show an excellent current density of 2066, 3047, and 1231 mA mgPd−1 for oxidation of ethanol, ethylene glycol, and glycerol, respectively. The “volcano-like” behaviors observed on PdBi TNWs for AORs indicate that the maximum catalytic mass activity is a well balance between active intermediates and blocking species at the interface. This study offers an effective and universal method to build novel nanocatalysts in various applications by rationally designing highly efficient catalysts with specific strain.

Single atom iron carbons supported Pd–Ni–P nanoalloy as a multifunctional electrocatalyst for alcohol oxidation

Exploring high-performance and multifunctional electrocatalysts for alcohols oxidation is the key to develop alkaline fuel cells. Herein, we prepared a novel palladium-nickel-phosphorus catalyst supported on single atom iron carbons (SAICs) with different diameter sizes (1000 nm, 200 nm, 100 nm, 50 nm, and 20 nm), which were synthesized by direct carbonization of Fe-doped Zeolitic Imidazolate Framework-8 (ZIF-8). Electrochemical tests reveal that the as-prepared PdNiP/50nmSAIC exhibited excellent electrooxidation activity and stability to the various alcohols (methanol, glycerol, and especially ethylene glycol) electrooxidation in the alkaline solution, which is much higher than that of commercial Pd/C and other advanced Pd-based catalysts. Meanwhile, the rotating disk electrode (RDE) and CO-stripping results proves that PdNiP/50nmSAIC possesses a faster kinetic process of ethylene glycol oxidation and enhanced anti-CO poisoning ability. Our efforts provide a new strategy for the development of MOFs-derived multielement electrocatalyst with excellent activity and stability, and a bright future for alcohol oxidation.

Coexistence of Au single atoms and Au nanoparticles on NiAl-LDH for selective electrooxidation of benzyl alcohol to benzaldehyde.

Introducing different active sites into heterogeneous catalysts provides new prospects to address the challenges in single-atom catalysis. Herein, the Au single atoms together and the Au nanoparticles were loaded onto NiAl-LDH by a facile impregnation-reduction method for the first time, resulting in the formation of Au1+n-NiAl-LDH, in which abundant Au single atoms are located around the Au nanoparticles with ∼5 nm size. When applied in the electrocatalytic benzyl alcohol oxidation reaction (BAOR), the as-prepared Au1+n-NiAl-LDH exhibits a remarkable selectivity of 91% and 177.63 μmol for benzaldehyde in 5 hours, while in contrast examples using solely Au single atom loaded NiAl-LDH (Au1-NiAl-LDH) and solely Au nanoparticle loaded NiAl-LDH (Aun-NiAl-LDH) can only realize 87.36 μmol production (75% selectivity) and 48.90 μmol production (28% selectivity) of benzaldehyde, respectively. Such a dramatic difference can be attributed to the synergistic effects of Au single atoms and Au nanoparticles. DFT calculation results reveal that for Au1+n-NiAl-LDH, Au single atoms promote the dehydrogenation capacity of LDH laminates, while Au nanoparticles offer adsorption sites for the electrophilic attachment of benzyl alcohol.

Exploration of active sites of ethyl alcohol electro-oxidation on porous gold nanoparticles with enhanced Raman spectroscopy.

Novel porous gold nanospheres are prepared by calcination of the gold-urea complexes. The enhanced Raman spectra of ethanol catalyzed by different doses of porous gold nanospheres are measured with a 532 nm laser as the excitation source, and an enhanced charge coupled device served in spectral detection and microscopic imaging. The electrochemical experiments show that the catalytic oxidation products of ethanol with porous gold nanoparticles are acetaldehyde, acetic acid, and water, which further proved that the porous gold nanoparticles can activate the -CH2 of ethanol.

A Liquid-Liquid-Solid System to Manipulate the Cascade Reaction for Highly Selective Electrosynthesis of Aldehyde.

Electrocatalytic synthesis of aldehydes from alcohols exhibits unique superiorities as a promising technology, in which cascade reactions are involved. However, the cascade reactions are severely limited by the low selectivity resulting from the peroxidation of aldehydes in a traditional liquid-solid system. Herein, we report a novel liquid-liquid-solid system to regulate the selectivity of benzyl alcohol electrooxidation. The selectivity of benzaldehyde increases 200-fold from 0.4 % to 80.4 % compared with the liquid-solid system at a high current density of 136 mA cm-2 , which is the highest one up to date. In the tri-phase system, the benzaldehyde peroxidation is suppressed efficiently, with the conversion of benzaldehyde being decreased from 87.6 % to 3.8 %. The as-produced benzaldehyde can be in situ extracted to toluene phase and separated from the electrolyte to get purified benzaldehyde. This strategy provides an efficient way to efficiently enhance the selectivity of electrocatalytic cascade reactions.

A Liquid‐Liquid‐Solid System to Manipulate the Cascade Reaction for Highly Selective Electrosynthesis of Aldehyde

AbstractElectrocatalytic synthesis of aldehydes from alcohols exhibits unique superiorities as a promising technology, in which cascade reactions are involved. However, the cascade reactions are severely limited by the low selectivity resulting from the peroxidation of aldehydes in a traditional liquid‐solid system. Herein, we report a novel liquid‐liquid‐solid system to regulate the selectivity of benzyl alcohol electrooxidation. The selectivity of benzaldehyde increases 200‐fold from 0.4 % to 80.4 % compared with the liquid‐solid system at a high current density of 136 mA cm−2, which is the highest one up to date. In the tri‐phase system, the benzaldehyde peroxidation is suppressed efficiently, with the conversion of benzaldehyde being decreased from 87.6 % to 3.8 %. The as‐produced benzaldehyde can bein situextracted to toluene phase and separated from the electrolyte to get purified benzaldehyde. This strategy provides an efficient way to efficiently enhance the selectivity of electrocatalytic cascade reactions.

Laccase mediated electrosynthesis of heliotropin on mango-kernel derived carbon nanosphere composite: A sustainable approach

Facile fabrication of enzyme immobilized carbon nanospheres (CNS) based catalysts with high electrical conductivity and catalytic efficiency are of decisive importance for their electrocatalysis. Herein, we report a novel, green and highly efficient synthesis route for the development of an electrode surface with enhanced electrical conductivity and better catalytic activity for the electrochemical synthesis of heliotropin. An important organic intermediate, heliotropin is widely employed in organic synthetic chemistry, perfume, pharmaceutical and dye industries. To design an efficient electrocatalyst, the obtained biowaste (mango seed kernels) was pyrolyzed and subjected to acid treatment to form functionalised CNS (f-CNS). The functionalised CFP electrode was employed as a template for laccase immobilization. This was further treated with free laccase resulting in the formation of Lac-fCNS/CFP electrode. The enzyme based catalytic effect of the developed electrode exhibited excellent electrooxidation of piperonyl alcohol in the presence of TEMPO, which served as the mediator. A high yield (72%) of heliotropin was achieved during the electrooxidation at 0.78 V via bulk electrolysis. The obtained product (heliotropin aka piperonal) was confirmed via 1 H NMR and 13 C NMR. Additionally, computational molecular docking analysis of f-CNS:laccase composite showed strong binding affinity (-6.2 kcal/mol) with TEMPO in comparison with free laccase (-5.1 kcal/mol). The excellent selectivity and efficiency of the developed electrocatalyst aims to surpass all other reported laccase-TEMPO mediated based electrocatalytic oxidation reactions. Effect of porosity obtained from carbon nanospheres might be the reason for the present investigations. • Facile synthesis of mango-seed kernel derived carbon nanospheres (CNS) via pyrolysis. • Laccase immobilization onto functionalized CNS, an effective carbon substrate for electrochemical synthesis. • Laccase-TEMPO mediated electrochemical oxidation of piperonyl alcohol to form heliotropin or piperonal. • A higher binding affinity observed in the interactions between the fabricated composite (Lac-fCNS) and TEMPO was studied by Molecular docking analysis.