Value-added Chemicals Research Articles

3D-Printed Hierarchical Nanostructured N-Co2NiO4 NF Electrode for Efficient Concurrent Electrocatalytic Production of Hydrogen and Formate.

Replacing the oxygen evolution reaction with the alternative glycerol electro-oxidation reaction (GER) provides a promising strategy to enhance the efficiency of hydrogen production via water electrolysis while co-generating high-value chemicals. However, obtaining low-cost and efficient GER electrocatalysts remains a big challenge. Herein, a self-supported N-doped Co2NiO4 nanoflakes (N-Co2NiO4 NF) is proposed for efficient electrocatalytic oxidation of glycerol to formate. The synergistic effect induced by the interaction of the layered Co2NiO4 nanostructures on the 3D-printed Nickel-Yttria-stabilized zirconia (Ni-YSZ) substrate and the amorphous nitrogen-doping promotes the anodic GER. The N-Co2NiO4 NF exhibits low potentials of 1.07 and 1.18V (vs. RHE) for GER to drive 10 and 50mAcm-2, respectively. The constituted two-electrode electrolyzer (N-Co2NiO4 NF//NiS-Co-NiP) displays excellent activity that only requires ultralow cell voltages of 1.24 and 1.55V to afford 10 and 200mAcm-2, respectively, with a high FE (97%) for formate production and an excellent durability (120h). This study provides a versatile approach for manufacturing high-performance Ni-based electrocatalyst for GER, paving the way for the energy-saving and environmentally-friendly co-production of value-added chemicals and hydrogen.

Titanium-Catalyzed Reaction of Silacyclobutanes with Alkenes: Mimicking the Reactivity and Reversing the Selectivity Towards Late Transition Metals.

Transition metal-catalyzed ring opening and expansion reactions of silacyclobutanes (SCBs) constitute an atom- and step-economical strategy to construct value-added silicon-containing chemicals. Despite extensive studies, the reaction of SCBs with simple alkenes has only one precedent. Moreover, most reported reactions of SCBs use late transition metals (Pd, Ni, Rh) as catalysts. By contrast, there are no reports of using early transition metals. Herein, we report the first example, to our knowledge, of early-transition-metal-catalyzed reactions of SCBs using earth's second abundant titanium as a catalyst. Notably, orthogonal selectivity was observed. Selective activation of the relatively inert C(sp3)-Si bond was achieved in the case of benzosilacyclobutenes, a selectivity that has rarely been achieved using other metals. Even for silacyclobutanes with C(sp3)-Si bonds only, our titanium system also shows complementary selectivity towards late transition metals to give distinct products. Thus, structurally varied SCBs and alkenes were reacted in our system to afford structurally diverse silicon-containing products that are otherwise difficult to obtain using other transition metals.

Advanced systems for enhanced CO2 electroreduction.

Carbon dioxide (CO2) electroreduction has extraordinary significance in curbing CO2 emissions while simultaneously producing value-added chemicals with economic and environmental benefits. In recent years, breakthroughs in designing catalysts, optimizing intrinsic activity, developing reactors, and elucidating reaction mechanisms have continuously driven the advancement of CO2 electroreduction. However, the industrialization of CO2 electroreduction remains a challenging task, with high energy consumption, high costs, limited reaction products, and restricted application scenarios being the issues that urgently need to be addressed. To accelerate the progress of CO2 electroreduction towards practical application, this review shifts the research focus from catalysts to aspects such as reactions and systems, aiming to improve reaction efficiency, reduce technical costs, expand the range of products, and enhance selectivity, offering readers a new perspective. In particular, innovative and specific design strategies such as CO2 reduction coupled with alternative oxidation, co-reduction reaction of CO2 and C/N/O/S-containing species, cascade systems, and integrated CO2 capture and reduction systems are discussed in detail. Additionally, personal views on the opportunities and future challenges of the aforementioned innovative strategies are provided, offering new insights for the future research and development of CO2 electroreduction.

Precise Separation of Complex Ultrafine Molecules through Solvating Two-Dimensional Covalent Organic Framework Membranes.

Isoporous nanomaterials, with their proven potential for accurate molecular sieving, are of substantial interest in propelling sustainable membrane techniques. Covalent organic frameworks (COFs) are prominent due to their customizable isopores and chemistry. Still, the discrepancy in experimental and theoretical structures poses a challenge to developing COF membranes for molecular separations. Here, we report high-selectivity sieving of complex ultrafine molecules through solvating pore-to-pore-aligned two-dimensional COF membranes. Our structurally oriented membrane shows reversible interlayer expansion with intralayer shift in response to solvent exposure. This dynamic deformation induced by solvents leads to a reduction in the aperture of the membrane's sieving pores, which correlates with the number of COF layers. The resultant membranes yield largely improved molecular selectivity to discriminate binary and trinary complex mixtures, exceeding the conventional COF membranes. The membrane's robustness against solvents and physical aging permits extremely stable microporosity and reliable operation for over 3000 h. This exceptional performance positions our membrane as an alternative to enriching and purifying value-added chemicals, such as active pharmaceutical ingredients.

Regulating Interfacial Hydrogen-Bonding Networks by Implanting Cu Sites with Perfluorooctane to Accelerate CO2 Electroreduction to Ethanol.

Efficient CO2 electroreduction (CO2RR) to ethanol holds promise to generate value-added chemicals and harness renewable energy simultaneously. Yet, it remains an ongoing challenge due to the competition with thermodynamically more preferred ethylene production. Herein, we presented a CO2 reduction predilection switch from ethylene to ethanol (ethanol-to-ethylene ratio of ~5.4) by inherently implanting Cu sites with perfluorooctane to create interfacial non-covalent interactions. The 1.83%F-Cu2O organic-inorganic hybrids (OIHs) exhibited an extraordinary ethanol faradaic efficiency (FEethanol) of ∼55.2%, with an impressive ethanol partial current density of 166 mA cm-2 and excellent robustness over 60 hours of continuous operation. This exceptional performance ranks our 1.83%F-Cu2O OIHs among the best-performing ethanol-oriented CO2RR electrocatalysts. Our findings identified that C8F18 could strengthen the interfacial hydrogen bonding connectivity, which consequently promotes the generation of active hydrogen species and preferentially favors the hydrogenation of *CHCOH to *CHCHOH, thus switching the reaction from ethylene-preferred to ethanol-oriented. The presented investigations highlight opportunities for using noncovalent interactions to tune the selectivity of CO2 electroreduction to ethanol, bringing it closer to practical implementation requirements.

1T/2H-MoS2/CdS heterojunction for the co-production of lactic acid photoreforming to hydrogen and value-added chemicals

Solar-driven photoreforming of biomass to obtain green and clean energy H2 and high value-added chemicals is one of the most promising approach to tackle problems concerning energy crisis and environmental pollution. To achieve this goal, the design and synthesis of photocatalysts with efficient photocatalysis and selectivity is a top priority. We synthesized lamellar composition of floral MoS2-modified CdS composites to reform biomass-derived lactic acid efficiently and selectively to tartaric acid derivatives, pyruvic acid and H2. During photocatalysis, there is accumulation of photogenerated electrons on MoS2 as a reduction center for hydrogen-extraction reaction. The holes on CdS activate α-C-H and α-O-H in lactic acid to form the carbon-centered radical ⋅CCH3(OH)COOH and the oxygen-centered radical ⋅OCH(CH3)COOH. ⋅CCH3(OH)COOH was preferentially adopted for the coupling pathway to yield tartaric acid derivatives, and ⋅OCH(CH3)COOH was further dehydrogenated to form pyruvic acid. The liquid phase product of CdS was dominated by tartaric acid derivatives with a maximum selectivity of 75.0%. The liquid phase product of CdS/MoS2-7% was dominated by pyruvic acid with a maximum selectivity of 80.0%.

Conversion of Spirulina platensis into Methanol via Gasification: Process Simulation Modeling and Economic Evaluation

The conversion of bioresources like Spirulina platensis (SP) into value-added chemicals, such as methanol, offers a sustainable replacement of fossil fuels and contributes to greenhouse gas mitigation. This study presents an integrated process simulation model, developed using Aspen Plus v10®, for the steam gasification of SP and subsequent methanol production. Process parameters, including temperature range from 650-950°C, steam/feed ratio from 0.5-2, and recycle ratio from 0-9, were investigated to optimize syngas composition and methanol yield. Results demonstrated that increasing temperature enhances H2 and CO production while reducing CO2 and CH4, significantly increasing methanol production from 6500 to 9500 kg/h. The steam/feed ratio also influences syngas composition and methanol yield, with higher ratios promoting H2 and CO2 production and reducing CO and CH4. The economic evaluation of two scenarios, a base case and an optimum case, shows that the capital expenditure (Capex) and operating expenditure (Opex) are 19.3M$ and 9.07M$ for the base case, and 20.018M$ and 10.21M$ for the optimum case. The analysis also reveals that the optimum case, with higher methanol production (7.2 tonnes/h compared to 6.7 tonnes/h in the base case), generates a higher net income (9.76 M$/y) and reduces CO2 emissions (4.918 tonnes CO2-e/y compared to 5.72 tonnes CO2-e/y). The energy flow indicates the input energy requirement, the energy carried by methanol, and the surplus energy, totalling 26740 kW to meet the major system's energy demands. This study provides valuable insights for researchers, policymakers, and commercial entities seeking to develop sustainable and economically viable biofuel production processes.

Selective light-driven methane oxidation to ethanol

Methane (CH4) photocatalytic upgrading to value-added chemicals, especially C2 products, is significant yet challenging due to sluggish energy/mass transfer and insufficient chemical driven-force in single photochemical process. Herein, we realize solar-driven CH4 oxidation to ethanol (C2H5OH) on crystalline carbon nitride (CCN) modified with Cu9S5 and Cu single atoms (Cu9S5/Cu-CCN). The integration of photothermal effect and photocatalysis overcomes CH4-to-C2H5OH conversion bottlenecks, with Cu9S5 as a hotspot to convert solar-energy to heat. In-situ characterizations demonstrate that Cu single atoms play as electron acceptor for O2 reduction to ·OOH/ · OH, while Cu9S5 acts as hole acceptor and site for CH4 adsorption, C − H activation, and C − C coupling. Theoretical calculations demonstrate that Cu9S5/Cu-CCN reduces C − C coupling energy barrier by stabilizing ·CH3 and ·CH2O. Impressively, C2H5OH productivity reaches 549.7 μmol g–1 h–1, with selectivity of 94.8% and apparent quantum efficiency of 0.9% (420 nm). This work provides a sustainable avenue for CH4 conversion to value-added chemcials.

Selective photooxidation of methane to C1 oxygenates by constructing heterojunction photocatalyst with mild oxidation ability

Selective photocatalytic aerobic oxidation of methane to value-added chemicals offers a promising pathway for sustainable chemical industry, yet remains a huge challenge owing to the consecutive overoxidation of primary products. Here, a type II heterojunction were constructed in Ag-AgBr/ZnO to reduce the oxidation potential of stimulated holes and prevent the undesirable CH4 overoxidation side reactions. For photocatalytic oxidation of methane under ambient temperature, the products yield of 1499.6 μmol gcat−1 h−1 with a primary products selectivity of 77.9% was achieved over Ag-AgBr/ZnO, which demonstrate remarkable improvement compared to Ag/ZnO (1089.9 μmol gcat−1 h−1, 40.1%). The superior activity and selectivity result from the promoted charge separation and the redox potential matching with methane activation after introducing AgBr species. Mechanism investigation elucidated that the photo-generated holes transferred from the valence band of ZnO to that of AgBr, which prevent H2O oxidation and enhance the selective generation of •OOH radical.

Synergistic interplay of CuOx and Pd nanodots on TiO2 for efficient and highly selective photocatalytic oxidation of CH4 to oxygenates with O2

Direct photocatalytic methane oxidation to produce liquid oxygenates offers a promising approach for the upgrading of abundant methane under mild conditions, yet it remains a formidable challenge in achieving high reaction rates while maintaining high selectivity. Herein, we report the highly dispersed CuOx and Pd nanodots decorated TiO2 for photocatalytic oxidation of CH4 with O2 at room temperature, which exhibits a remarkable C1 oxygenates production rate of 39.5 mmol·g−1·h−1 with a nearly 100 % selectivity, outperforming most of the state-of-the-art photocatalysts. Both experimental and theoretical studies suggest that the impressive photocatalytic performance is attributed to the synergy of Cu+ species and Pd nanodots. Cu+ species not only promote the interfacial electrons transfer from TiO2 to Pd, but also mediate CH4 oxidation reaction to avoid overoxidation of oxygenates to CO2, while the resulting electron-rich Pd sites boost the production of primary products (CH3OOH and CH3OH) by lowering the reaction energy. This work provides a new pathway for developing highly efficient photocatalysts for the selective conversion of methane to value-added chemicals by designing bimetallic cocatalysts.

High-valence molybdenum doped Ni(OH)2 nanosheets enhancing hydrogen production and glycerol oxidation to formic acid

The glycerol electrooxidation reaction (GEOR) replacing the anodic oxygen evolution reaction (OER) in water splitting is an effective strategy for hydrogen production and high value-added chemicals in an energy-saving manner in recent years. The key to this technology is to design efficient electrocatalysts to enhance the GEOR activity and effectively regulate product selectivity. Herein, a high-valence metal Mo-doped Ni(OH)2 nanosheets (Mo-Ni(OH)2/NF) was in-situ grown on the nickel foam (NF) for enhancing hydrogen production and glycerol oxidation to formic acid. The Mo-Ni(OH)2/NF exhibits unique network nanosheet morphology with large specific surface area and electron conduction, which is beneficial for exposing more active sites for reactions and promoting the mass transfer of electrolytes and products. The synergistic interaction between Mo and Ni facilitates the regulation of the electronic structure of the catalyst, and accelerates the reaction kinetics. When the Mo-Ni(OH)2/NF−1 is assembled into an overall glycerol-water splitting system, a low voltage of only 1.36 V is required to achieve a current density of 10 mA cm−2, which is 290 mV lower than the cell voltage needed for traditional water splitting under the same conditions.

Direct low concentration CO2 electroreduction to multicarbon products via rate-determining step tuning

Direct converting low concentration CO2 in industrial exhaust gases to high-value multi-carbon products via renewable-energy-powered electrochemical catalysis provides a sustainable strategy for CO2 utilization with minimized CO2 separation and purification capital and energy cost. Nonetheless, the electrocatalytic conversion of dilute CO2 into value-added chemicals (C2+ products, e.g., ethylene) is frequently impeded by low CO2 conversion rate and weak carbon intermediates’ surface adsorption strength. Here, we fabricate a range of Cu catalysts comprising fine-tuned Cu(111)/Cu2O(111) interface boundary density crystal structures aimed at optimizing rate-determining step and decreasing the thermodynamic barriers of intermediates’ adsorption. Utilizing interface boundary engineering, we attain a Faradaic efficiency of (51.9 ± 2.8) % and a partial current density of (34.5 ± 6.4) mA·cm−2 for C2+ products at a dilute CO2 feed condition (5% CO2 v/v), comparing to the state-of-art low concentration CO2 electrolysis. In contrast to the prevailing belief that the CO2 activation step (CO2+e−+*→CO2−*\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{CO}}_{2}+{e}^{-}+\\, * \\,\ o {}^{ * }{CO}_{2}^{-}$$\\end{document}) governs the reaction rate, we discover that, under dilute CO2 feed conditions, the rate-determining step shifts to the generation of *COOH (CO2−*+H2O→C*OOH+OH−(aq)\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${}^{ * } {{CO}}_{2}^{-}+{H}_{2}O\ o {}^{ * } {COOH}+{{OH}}^{-}({aq})$$\\end{document}) at the Cu0/Cu1+ interface boundary, resulting in a better C2+ production performance.

Transcriptomic analysis identifies a furfural reductase in Lactiplantibacillus plantarum

Lignocellulosic biomass (LCB) is a promising feedstock for producing value-added chemicals, with Lactiplantibacillus plantarum emerging as a potential cell factory due to its ability to metabolize lignocellulosic sugars. However, LCB preprocessing generates toxic compounds, such as furfural and 5-hydroxymethylfurfural (HMF), which inhibit microbial growth. In this study, we explored the transcriptional responses of L. plantarum JGR2 to furfural, HMF, and their combination using RNA-seq analysis. Notably, the pyr operon, involved in pyrimidine metabolism, was downregulated across all treatments, while 1,3-propanediol dehydrogenase (dhaT) was upregulated under furfural exposure. Recombinant E. coli overexpressing DhaT successfully converted furfural into the less toxic furfuryl alcohol. The identification of DhaT as a furfural reductase, along with the transcriptomic data on L. plantarum's response to furan aldehydes, can guide the development of LCB-driven L. plantarum as a novel microbial cell factory.

Electrochemical upgrading of PET plastic wastes for hydrogen production using porous Fe–Ni2P nanosheets

The electrochemical upgrading of PET plastic wastes-to-hydrogen is an important conversion system for achieving sustainable, low-cost and scalable hydrogen production. Designing cost-effective and highly active dual-function electrocatalysts for the ethylene glycol (PET monomer) oxidation reaction (EGOR) and hydrogen evolution reaction (HER) is very crucial for achieving practical application of PET plastic wastes upgrading assisted electrochemical water splitting technology. Herein, a simple hydrothermal-phosphating two-step method is implemented to achieve ultrathin porous iron (Fe) doped nickel phosphide (Ni2P) nanosheets attached to the nickel foam (named as Fe–Ni2P/NF). Profiting from the ample active sites provided by the ultrathin structure, porous structure and the optimized electronic structure caused by Fe doping, Fe–Ni2P/NF exhibits predominant electroactivity for HER and EGOR. Additionally, PET plastic wastes hydrolysate electrolyzer is assembled by using Fe–Ni2P/NF as a dual-functional electrode for the co-generation of hydrogen and formate. The constructed Fe–Ni2P/NF||Fe–Ni2P/NF electrolyzer only requires an electrolysis potential of 1.39 V to derive 10 mA cm−2 current density, which is lower than that of conventional water splitting (1.55 V). This work would afford a reference for constructing cost-efficient and steady plastic-assisted water electrolysis bifunctional catalysts, and expands the field of energy-saving co-generation of value-added chemicals and hydrogen.

Steering Acid-Base Site Distribution and Hydrophobicity of Bioresourced Bifunctional Hybrid Materials for Direct Synthesis of γ-Valerolactone from Biomass-Based Furfural.

The direct production of value-added chemicals from biomass via multiple conversion processes with a sole renewable solid catalyst is promising for carbon-neutral development while challenging. Herein, a series of novel bioresourced organic-inorganic hybrid materials were synthesized from bio-based ascorbic acid (Vc), zirconium chloride (ZrCl4) and p-toluenesulfonic acid (p-TSA) through a facile solvothermal process. The as-prepared Zr-Vc-3 catalyst with Vc, ZrCl4, and p-TSA in the 1 : 1:0.5 molar ratio displayed outstanding performance in direct furfural-to-γ-valerolactone (GVL) transformation, giving an ultrahigh GVL yield of 76.2 %, with an ideal activation energy (55.46 kJ mol-1), outperforming state-of-the-art catalysts. The superior performance of Zr-Vc-3 could be ascribed to its good reusability, relatively large pore size, suitable amount of acid-base sites, and good hydrophobicity. Mechanistic studies unveiled that Lewis acid-base sites facilitate the conversion of furfural to furfuryl alcohol and isopropyl levulinate (IPL) to 4-hydroxypentanoate via transfer hydrogenation process, while Brønsted acid sites are instrumental in the ring-opening of furfuryl alcohol to IPL and the lactonization of 4-hydroxypentanoate to GVL, overall contributing to the multi-step conversion of furfural to GVL in a single pot. This work provides a valuable reference for precisely constructing bio-based OIHMs with tailored functionalities for the one-pot valorization of biomass feedstocks via tandem reactions.

Electroreforming of plastic wastes for value-added products.

The problem of plastic pollution is becoming increasingly serious, and there is an urgent need to reduce the use of plastics and to improve the recovery rate of plastic wastes. Plastic wastes can be transformed into value-added chemicals at the anode through electrocatalytic conversion, while coupling with cathodic reduction reactions to achieve cogeneration of valuable anodic and cathodic products. The plastic electroreforming technology has unprecedented advantages, including a green and decentralizable process, renewable energy storage, ecological benefits, resource recovery, cost-effectiveness, and so on. Herein, we present a mini review about recent advances in this topic. We first discuss the electrooxidation mechanisms of different plastic wastes (such as polylactic acid, polyethylene glycol terephthalate, polyethylene, polyethylene furanoate, polybutylene terephthalate, and polyamides). Then, the progress of plastic waste-assisted electrolysis systems is summarized, including plastic waste-assisted water splitting for hydrogen production and oxygen reduction, as well as plastic electroreforming coupled with CO2 reduction, and the nitrate reduction reaction. Finally, the development prospects and challenges in this field are introduced and discussed. This review aims to provide a concise overview of the emerging plastic electroreforming, thus offering insight on the design of efficient and stable plastic-assisted electrolysis systems.

Selective oxidation of glycerol to value-added chemicals over green carbon dots modified graphitic carbon nitride charge-transfer photocatalyst

Selective oxidation of glycerol to value-added chemicals over green carbon dots modified graphitic carbon nitride charge-transfer photocatalyst

Closing the Loop in the Carbon Cycle: Enzymatic Reactions Housed in Metal-Organic Frameworks for CO2 Conversion to Methanol.

The preparation of value-added chemicals from carbon dioxide (CO2) can act as a way of reducing the greenhouse gas from the atmosphere. Industrially significant C1 chemicals like methanol (CH3OH), formic acid (HCOOH), and formaldehyde (HCHO) can be formed from CO2. One sustainable way of achieving this is by connecting the reactions catalyzed by the enzymes formate dehydrogenase (FDH), formaldehyde dehydrogenase (FALDH), and alcohol dehydrogenase (ADH) into a single cascade reaction where CO2 is hydrogenated to CH3OH. For this to be adaptable for industrial use, the enzymes should be immobilized in materials that are extraordinarily protective of the enzymes, inexpensive, stable, and of ultra-large surface area. Metal-organic frameworks (MOFs) meet these criteria and are expected to usher in the much-awaited dispensation of industrial biocatalysis. Unfortunately, little is known about the molecular behaviour of MOF-immobilized FDH, FALDH, and ADH. It is also yet not known which MOFs are most promising for industrial enzyme-immobilization since the field of reticular chemistry is growing exponentially with millions of hypothetical and synthesized MOF structures reported at present. This review initially discusses the properties of the key enzymes required for CO2 hydrogenation to methanol including available cofactor regeneration strategies. Later, the characterization techniques of enzyme-MOF composites and the successes or lack thereof of enzyme-MOF-mediated CO2 conversion to CH3OH and intermediate products are discussed. We also discuss reported multi-enzyme-MOF systems for CO2 conversion cognizant of the fact that at present, these systems are the only chance of housing cascade-type biochemical reactions where strict substrate channelling and operational conditions are required. Finally, we delve into future perspectives.

Efficient electrocatalysis conversion of glycerol to formate in alkaline solution by nickel (oxy)hydroxide supported cobalt nanoneedle arrays

Electrochemical oxidation of glycerol into value-added chemicals represents a sustainable approach for not only valorizing biomass resources but also improving the energy efficiency of electrolysis by replacing the kinetically sluggish oxidation of water at the anode. Here, we present a nickel (oxy)hydroxide supported cobalt nanoneedle arrays catalyst (CoNA-NiOH/NF-2) for effective oxidation of glycerol. The loaded Co(OH)2 forms more oxygen defects, increases the active sites, and enhances the performance of glycerol oxidation. The CoNA-NiOH/NF-2 catalyst significantly reduces energy consumption by achieving a current density of 10 mA cm−2 at a low voltage of 1.22 V vs. RHE, and 100 mA cm−2 at 1.42 V vs. RHE, which is approximately 240 mV lower than oxygen evolution reaction (OER). Additionally, the Faraday efficiency of formate generation reached 98 %. The growth of renewable energy sources will greatly benefit from this strategy, which calls for replacing anodic OER with biomass oxidation.

Highly active cobalt oxide-palladium nanohybrid catalyst enables selective electrocatalytic synthesis of glycolic acid

Glycolic acid is a unique value-added chemical, while its large-scale production is limited by harsh synthesis conditions and poor selectivity. Herein, we have ingeniously constructed a highly active cobalt oxide-supported palladium electrocatalyst on nickel foam (Pd-Co3O4/NF) for ethylene glycol oxidation to glycolic acid with a high Faradaic efficiency (93.1 %) at ultra-low potential (0.9 V vs. RHE). In situ Fourier transform infrared spectroscopy revealed the pathway of ethylene glycol oxidation reaction (EGOR). The theoretical results reveal that Co3O4/NF can effectively promote the formation of *OH and weaken the adsorption of toxic *CO intermediates on Pd-Co3O4/NF. And the downshifted d-band center of Pd-Co3O4/NF is inducive to facilitate the desorption of GA from the Pd surface, prevents the excessive oxidation thus improving the selectivity. Moreover, Pd-Co3O4/NF exhibits considerable anode current density with respect to electro-reforming polyethylene terephthalate (PET)-derived EG oxidation, accompanied by the generation of green hydrogen at the cathode. This work puts forward an innovative approach for catalyst construction toward EGOR and highlights the strategy of electro-upcycling of PET.