Efficient asymmetric diffusion channel in MnCo2O4 spinel for ammonium-ion batteries.

Transition metal oxides ion diffusion channels have been developed for ammonium-ion batteries (AIBs). However, the influence of microstructural features of diffusion channels on the storage and diffusion behavior of NH4+ is not fully unveiled. In this study, by using MnCo2O4 spinel as a model electrode, the asymmetric ion diffusion channels of MnCo2O4 have been regulated through bond length optimization strategy and investigate the effect of channel size on the diffusion process of NH4+. In addition, the reducing channel size significantly decreases NH4+ adsorption energy, thereby accelerating hydrogen bond formation/fracture kinetics and NH4+ reversible diffusion within 3D asymmetric channels. The optimized MnCo2O4 with oxygen vacancies/carbon nanotubes composite exhibits impressive specific capacity (219.2 mAh g-1 at 0.1 A g-1) and long-cycle stability. The full cell with 3,4,9,10-perylenetetracarboxylic diimide anode demonstrates a remarkable energy density of 52.3 Wh kg-1 and maintains 91.9% capacity after 500 cycles. This finding provides a unique approach for the development of cathode materials in AIBs.

Crystallinity engineering for overcoming the activity-stability tradeoff of spinel oxide in Fenton-like catalysis.

A precise modulation of heterogeneous catalysts in structural and surface properties promises the development of more sustainable advanced oxidation water purification technologies. However, while catalysts with superior decontamination activity and selectivity are already achievable, maintaining a long-term service life of such materials remains challenging. Here, we propose a crystallinity engineering strategy to break the activity-stability tradeoff of metal oxides in Fenton-like catalysis. The amorphous/crystalline cobalt-manganese spinel oxide (A/C-CoMnOx) provided highly active, hydroxyl group-rich surface, with moderate peroxymonosulfate (PMS)-binding affinity and charge transfer energy and strong pollutant adsorption, to trigger concerted radical and nonradical reactions for efficient pollutant mineralization, thereby alleviating the catalyst passivation by oxidation intermediate accumulation. Meanwhile, the surface-confined reactions, benefited from the enhanced adsorption of pollutants at A/C interface, rendered the A/C-CoMnOx/PMS system ultrahigh PMS utilization efficiency (82.2%) and unprecedented decontamination activity (rate constant of 1.48 min-1) surpassing almost all the state-of-the-art heterogeneous Fenton-like catalysts. The superior cyclic stability and environmental robustness of the system for real water treatment was also demonstrated. Our work unveils a critical role of material crystallinity in modulating the Fenton-like catalytic activity and pathways of metal oxides, which fundamentally improves our understanding of the structure-activity-selectivity relationships of heterogeneous catalysts and may inspire material design for more sustainable water purification application and beyond.

Electron delocalization triggers nonradical Fenton-like catalysis over spinel oxides.

Nonradical Fenton-like catalysis offers opportunities to overcome the low efficiency and secondary pollution limitations of existing advanced oxidation decontamination technologies, but realizing this on transition metal spinel oxide catalysts remains challenging due to insufficient understanding of their catalytic mechanisms. Here, we explore the origins of catalytic selectivity of Fe-Mn spinel oxide and identify electron delocalization of the surface metal active site as the key driver of its nonradical catalysis. Through fine-tuning the crystal geometry to trigger Fe-Mn superexchange interaction at the spinel octahedra, ZnFeMnO4 with high-degree electron delocalization of the Mn-O unit was created to enable near 100% nonradical activation of peroxymonosulfate (PMS) at unprecedented utilization efficiency. The resulting surface-bound PMS* complex can efficiently oxidize electron-rich pollutants with extraordinary degradation activity, selectivity, and good environmental robustness to favor water decontamination applications. Our work provides a molecule-level understanding of the catalytic selectivity and bimetallic interactions of Fe-Mn spinel oxides, which may guide the design of low-cost spinel oxides for more selective and efficient decontamination applications.

Controlling inversion disorder in a stoichiometric spinel magnet.

In the study of frustrated quantum magnets, it is essential to be able to control the nature and degree of site disorder during the growth process, as many measurement techniques are incapable of distinguishing between site disorder and frustration-induced spin disorder. Pyrochlore-structured spinel oxides can serve as model systems of geometrically frustrated three-dimensional quantum magnets; however, the nature of the magnetism in one well-studied spinel, ZnFe2O4, remains unclear. Here, we demonstrate simultaneous control of both stoichiometry and inversion disorder in the growth of ZnFe2O4 single crystals, directly yielding a revised understanding of both the collective spin behavior and lattice symmetry. Crystals grown in the stoichiometric limit with minimal site inversion disorder contravene all the previously suggested exotic spin phases in ZnFe2O4. Furthermore, the structure is confirmed on the [Formula: see text] space group with broken inversion symmetry that induces antiferroelectricity. The effective tuning of magnetic behavior by site disorder in the presence of robust antiferroelectricity makes ZnFe2O4 of special interest to multiferroic devices.

Effect of Oxidative Synthesis Conditions on the Performance of Single-Crystalline LiMn2- x Mx O4 (M = Al, Fe, and Ni) Spinel Cathodes in Lithium-Ion Batteries.

LiMn2 O4 (LMO) spinel cathode materials attract much interest due to the low price of manganese and high power density for lithium-ion batteries. However, the LMO cathodes suffer from the Mn dissolution problem at particle surfaces, which accelerates capacity fade. Herein, the authors report that the oxidative synthesis condition is a key factor in the cell performance of single-crystalline LiMn2- x Mx O4 (0.03 ≤ x ≤ 0.1, M = Al, Fe, and Ni) cathode materials prepared at 1000 °C. The use of oxygen flow during the spinel-phase formation minimizes the presence of oxygen vacancies generated at 1000 °C, thereby yielding a stoichiometrically doped LMO product; otherwise, the spinel cathode prepared in atmospheric air readily loses capacity due to the oxygen vacancies in the structure. As a way of circumventing the use of oxygen flow, a one-pot, two-step heating in air at 1000 °C and subsequently at 600 °C is used to yield the stoichiometric LMO product. The lithiation heating at 1000-600 °C resulted in a significant improvement in the cycling stability of the prepared LMO cathode in graphite-based full cells. This study on oxidative synthesis conditions also confirms the advantage of minimizing the surface area of the cathode particles.

N-Decorated Main-Group MgAl2O4 Spinel: Unlocking Exceptional Oxygen Reduction Activity for Zn-Air Batteries.

The development of economical and efficient oxygen reduction reaction (ORR) catalysts is crucial to accelerate the widespread application rhythm of aqueous rechargeable zinc-air batteries (ZABs). Here, a strategy is reported that the modification of the binding energy for reaction intermediates by the axial N-group converts the inactive spinel MgAl2O4 into the active motif of MgAl2O4-N. It is found that the introduction of N species can effectively optimize the electronic configuration of MgAl2O4, thereby significantly reducing the adsorption strength of *OH and boosting the reaction process. This main-group MgAl2O4-N catalyst exhibits a high ORR activity in a broad pH range from acidic and alkaline environments. The aqueous ZABs assembled with MgAl2O4-N shows a peak power density of 158.5 mW cm-2, the long-term cyclability over 2000 h and the high stability in the temperature range from -10 to 50 °C, outperforming the commercial Pt/C in terms of activity and stability. This work not only serves as a significant candidate for the robust ORR electrocatalysts of aqueous ZABs, but also paves a new route for the effective reutilization of waste Mg alloys.

FeNi2S4-A Potent Bifunctional Efficient Electrocatalyst for the Overall Electrochemical Water Splitting in Alkaline Electrolyte.

For a carbon-neutral society, the production of hydrogen as a clean fuel through water electrolysis is currently of great interest. Since water electrolysis is a laborious energetic reaction, it requires high energy to maintain efficient and sustainable production of hydrogen. Catalytic electrodes can reduce the required energy and minimize production costs. In this context, herein, a bifunctional electrocatalyst made from iron nickel sulfide (FeNi2S4 [FNS]) for the overall electrochemical water splitting is introduced. Compared to Fe2NiO4 (FNO), FNS shows a significantly improved performance toward both OER and HER in alkaline electrolytes. At the same time, the FNS electrode exhibits high activity toward the overall electrochemical water splitting, achieving a current density of 10 mA cm-2 at 1.63 V, which is favourable compared to previously published nonprecious electrocatalysts for overall water splitting. The long-term chronopotentiometry test reveals an activation followed by a subsequent stable overall cell potential at around 2.12 V for 20 h at 100 mA cm-2.

Iron 3D-Orbital Configuration Dependent Electron Transfer for Efficient Fenton-Like Catalysis.

Transition metals are excellent active sites to activate peroxymonosulfate (PMS) for water treatment, but the favorable electronic structures governing  reaction mechanism still remain elusive. Herein, the authors construct typical d-orbital configurations on iron octahedral (FeOh ) and tetrahedral (FeTd ) sites in spinel ZnFe2 O4 and FeAl2 O4 , respectively. ZnFe2 O4 (136.58 min-1 F-1 cm2 ) presented higher specific activity than FeAl2 O4 (97.47 min-1 F-1 cm2 ) for tetracycline removal by PMS activation. Considering orbital features of charge amount, spin state, and orbital arrangement by magnetic spectroscopic analysis, ZnFe2 O4 has a larger bond order to decompose PMS. Using this descriptor, high-spin FeOh is assumed to activate PMS mainly to produce nonradical reactive oxygen species (ROS) while high-spin FeTd prefers to induce radical species. This hypothesis is confirmed by the selective predominant ROS of 1 O2 on ZnFe2 O4 and O2 •- on FeAl2 O4 via quenching experiments. Electrochemical determinations reveal that FeOh has superior capability than FeTd for feasible valence transformation of iron cations and fast interfacial electron transfer. DFT calculations further suggest octahedral d-orbital configuration of ZnFe2 O4 is beneficial to enhancing Fe-O covalence for electron exchange. This work attempts to understand the d-orbital configuration-dependent PMS activation to design efficient catalysts.

Interphase Stabilization of LiNi0.5 Mn1.5 O4 Cathode for 5 V-Class All-Solid-State Batteries.

Employing high voltage cobalt-free spinel LiNi0.5 Mn1.5 O4 (LNMO) as a cathode is promising for high energy density and cost-effectiveness, but it has challenges in all-solid-state batteries (ASSBs). Here, it is revealed that the limitation of lithium argyrodite sulfide solid electrolyte (Li6 PS5 Cl) with the LNMO cathode is due to the intrinsic chemical incompatibility and poor oxidative stability. Through a careful analysis of the interphase of LNMO, it is elucidated that even the halide solid electrolyte (Li3 InCl6 ) with high oxidative stability can be decomposed to form resistive interphase layers with LNMO in ASSBs. Interestingly, with Fe-doping and a Li3 PO4 protective layer coating, LNMO with Li3 InCl6 displays stable cycle performance with a stabilized interphase at a high voltage (≈4.7 V) in ASSBs. The enhanced interfacial stability with the extended electrochemical stability window through doping and coating enables high electrochemical stability with LNMO in ASSBs. This work provides guidance for employing high-voltage cathodes in ASSBs and highlights the importance of stable interphases to enable stable cycling in ASSBs.

Fluorine Induced In Situ Formation of High Valent Nickel Species for Ultra Low Potential Electrooxidation of 5-Hydroxymethylfurfural.

The Nickel-based catalysts have a good catalytic effect on the 5-hydroxymethylfurfural electrooxidation reaction (HMFOR), but limited by the conversion potential of Ni2+ /Ni3+ , 1.35 V versus RHE, the HMF electrooxidation potential of nickel-based catalysts is generally greater than 1.35 V versus RHE. Considering fluorine has the highest Pauling electronegativity and similar atomic radius of oxygen, the introduction of fluorine into the lattice of metal oxides might promote the adsorption of intermediate species, thus improving the catalytic performance. F is successfully doped into the lattice structure of NiCo2 O4 spinel oxide by the strategy of hydrothermal reaction and low-temperature fluorination. As is confirmed by in situ electrochemical impedance spectroscopy and Raman spectroscopy, the introduction of F weakens the interaction force of metal-oxygen covalent bonds of the asymmetric MT -O-MO backbone and improves the valence of Ni in tetrahedra structure, which makes it easier to be oxidized to higher valence active Ni3+ under the action of electric field and promotes the adsorption of OH- , while the decrease of Co valence enhances the adsorption of HMF with the catalyst. Combining the above reasons, F-NiCo2 O4 shows superb electrocatalytic performance with a potential of only 1.297 V versus RHE at a current density of 20 mA cm-2 , which is lower than the most catalyst.

Microstructural Insights into Performance Loss of High-Voltage Spinel Cathodes for Lithium-ion Batteries.

Spinel-structured LiNix Mn2-x O4 (LNMO), with low-cost earth-abundant constituents, is a promising high-voltage cathode material for lithium-ion batteries. Even though extensive electrochemical investigations have been conducted on these materials, few studies have explored correlations between their loss in performance and associated changes in microstructure. Here, down to the atomic scale, the structural evolution of these materials is investigated upon the progressive cycling of lithium-ion cells. Transgranular cracking is revealed to be a key feature during cycling; this cracking is initiated at the particle surface and leads to the penetration of electrolytes along the crack path, thereby increasing particle exposure to the electrolyte. The lattice structure on the crack surface shows spatial variances, featuring a top layer of rock-salt, a sublayer of a Mn3 O4 -like arrangement, and then a mixed-cation region adjacent to the bulk lattice. The transgranular cracking, along with the emergence of local lattice distortion, becomes more evident with extended cycling. Further, phase transformation at primary particle surfaces and void formation through vacancy condensation is found in the cycled samples. All these features collectively contribute to the performance degradation of the battery cells during electrochemical cycling.

Structure and Electron Engineering for Nitrate Electrocatalysis to Ammonia: Identification and Modification of Active Sites in Spinel Oxides.

Cobalt spinel oxides, which consist of tetrahedral site (AO4) and octahedral site (BO6), are a potential group of transition metal oxides (TMO) for electrocatalytic nitrate reduction reactions to ammonia (NRA). Identifying the true active site in spinel oxides is crucial to designing advanced catalysts. This work reveals that the CoO6 site is the dominant site for NRA through the site substitution strategy. The suitable electronic configuration of Co at the octahedral site leads to a stronger interaction between the Co d-orbital and the O p-orbital in O-containing intermediates, resulting in a high-efficiency nitrate-to-ammonia reduction. Furthermore, the substitution of metallic elements at the AO4 site can affect the charge density at the BO6 site via the structure of A-O-B. Thereafter, Ni and Cu are introduced to replace the tetrahedral site in spinel oxides and optimize the electronic structure of CoO6. As a result, NiCo2O4 exhibits the best activity for NRA with an outstanding yield of NH3 (15.49 mg cm-2 h-1) and FE (99.89%). This study introduces a novel paradigm for identifying the active site and proposes an approach for constructing high-efficiency electrocatalysts for NRA.

A Doping-Induced SrCo0.4Fe0.6O3/CoFe2O4 Nanocomposite for Efficient Oxygen Evolution in Alkaline Media.

Perovskite and spinel oxides are promising alternatives to noble metal-based electrocatalysts for oxygen evolution reaction (OER). Herein, a novel perovskite/spinel nanocomposite comprised of SrCo0.4Fe0.6O3 and CoFe2O4 (SCF/CF) is prepared through a simple one-step method that incorporates iron doping into a SrCoO3- δ matrix, circumventing complex fabrication processes typical of these materials. At a Fe dopant content of 60%, the CoFe2O4 spinel phase is directly precipitated from the parent SrCo0.4Fe0.6O3 perovskite phase and the number of active B-site metals (Co/Fe) in the parent SCF can be maximized. This nanocomposite exhibits a remarkable OER activity in alkaline media with a small overpotentional of 294 mV at 10 mA cm-2. According to surface states analysis, the parent SCF perovskite remains in its pristine form under alkaline OER conditions, serving as a stable substrate, while the second spinel CF is covered by 5/8 monolayer (ML) O*, exhibiting considerable affinity toward the oxygen species involved in the OER. Analysis based on advanced OER microkinetic volcano model indicates that a 5/8 ML O* covered-CF is the origin for the remarkable activity of this nanocomposite. The results reported here significantly advance knowledge in OER and can boost application, scale-up and commercialisation of electrocatalytic technologies toward clean energy devices.

Sulfurized NiFe2O4 Electrocatalyst with In Situ Formed Fe-NiOOH Nanoparticles to Realize Industrial-Level Oxygen Evolution.

Constructing composite catalysts with refined geometric control and optimal electronic structure provides a promising route to enhance electrocatalytic performance toward the oxygen evolution reaction (OER). Herein, a composite catalyst is prepared with multiple components using chemical vapour deposition method to transform crystalline NiFe2O4 into crystalline NiFe2O4@amorphous S-NiFe2O4 with core-shell structure (C-NiFe2O4@A-S-NiFe2O4), and Fe-NiOOH nanoparticles are subsequently in situ generated on its surface during the process of electrocatalytic OER. The C-NiFe2O4@A-S-NiFe2O4 catalyst exhibits a low overpotential of 275 mV while possessing an excellent stability for 500 h at 10 mA cm-2. The anion exchange membrane water electrolyzer with C-NiFe2O4@A-S-NiFe2O4 anode catalyst obtains a current density of 4270 mA cm- 2 at 2.0 V. Further, in situ Raman spectroscopy result demonstrates that in situ generated Fe-NiOOH nanoparticles are revealed to act as the catalytic active phase for catalyzing the OER. Besides, introducing A-S-NiFe2O4 in C-NiFe2O4@A-S-NiFe2O4 facilitates the formation of Fe-NiOOH nanoparticles with high-valency Ni, thus increasing the proportion of lattice oxygen-participated OER. This work not only provides an alternative strategy for the design of high-performance catalysts, but also lays a foundation for the exploration of catalytic mechanisms.

Tuning Octahedron Sites of CoV2O4 via Cationic Competition for Efficient Oxygen Evolution Reaction.

Doping transition metal oxide spinels with metal ions represents a significant strategy for optimizing the electronic structure of electrocatalysts. Herein, a bimetallic Fe and Ru doping strategy to fine-tune the crystal structure of CoV2O4 spinel for highly enhanced oxygen evolution reaction (OER) is presented performance. The incorporation of Fe and Ru is observed at octahedral sites within the CoV2O4 structure, effectively modulating the electronic configuration of Co. Density functional theory calculations have confirmed that Fe acts as a novel reactive site, replacing V. Additionally, the synergistic effect of Fe, Co, and Ru effectively optimizes the Gibbs free energy of the intermediate species, reduces the reaction energy barrier, and accelerates the kinetics toward OER. As expected, the best-performing CoVFe0.5Ru0.5O4 displays a low overpotential of 240 mV (@10 mA cm-2) and a remarkably low Tafel slope of 38.9 mV dec-1, surpassing that of commercial RuO2. Moreover, it demonstrates outstanding long-term durability lasting for 72 h. This study provides valuable insights for the design of highly active polymetallic spinel electrocatalysts for energy conversion applications.

Low-Cost Self-Reconstructed High Entropy Oxide as an Ultra-Durable OER Electrocatalyst for Anion Exchange Membrane Water Electrolyzer.

Future energy loss can be minimized to a greater extent via developing highly active electrocatalysts for alkaline water electrolyzers. Incorporating an innovative design like high entropy oxides, dealloying, structural reconstruction, in situ activation can potentially reduce the energy barriers between practical and theoretical potentials. Here, a Fd-3m spinel group high entropy oxide is developed via a simple solvothermal and calcination approach. The developed (FeCoMnZnMg)3O4 electrocatalyst shows a near equimolar distribution of all the metal elements resulting in higher entropy (ΔS ≈1.61R) and higher surface area. The self-reconstructed spinel high entropy oxide (S-HEO) catalyst exhibited a lower overpotential of 240 mV to reach 10 mA cm-2 and enhanced reaction kinetics (59 mV dec-1). Noticeably, the S-HEO displayed an outstanding durability of 1000 h without any potential loss, significantly outperforming most of the reported OER electrocatalysts. Further, S-HEO is evaluated as the anode catalyst for an anion exchange membrane water electrolyzer (AEMWE) in 1 m, 0.1 m KOH, and DI water at 20 and 60 °C. These results demonstrate that S-HEO is a highly attractive, non-noble class of materials for high active oxygen evolution reaction (OER) electrocatalysts allowing fine-tuning beyond the limits of bi- or trimetallic oxides.

Near-Infrared Mechanoluminescence from Cr3+-Doped Spinel Nanoparticles for Potential Oral Diseases Detection.

Mechanoluminescence (ML) phosphors have found various promising utilizations such as in non-destructive stress sensing, anti-counterfeiting, and bio stress imaging. However, the reported NIR MLs have predominantly been limited to bulky particle size and weak ML intensity, hindering the further practical applications. For this regard, a nano-sized ZnGa2O4: Cr3+ NIR ML phosphor is synthesized by hydrothermal method. By improving the synthesis method and regulating the chemical composition, the NIR ML (600-1000 nm) intensity of such nano-materials has been further enhanced about four times. The reasons for the ML performance difference between micro-/nano- sized phosphors also have been preliminarily analyzed. Additionally, this work probes into the ML mechanism deeply in traps' aspect from band structure and defect formation energy, which can supply significant references for a new approach to develop efficient NIR ML nanoparticles. Finally, due to excellent tissue penetration capability, nano-sized ZnGa2O4:Cr3+ NIR ML phosphor shows great potential applications in biomedical fields such as for the detection of clinical oral diseases.

Amorphous/Crystalline Phases Mixed Nanosheets Array Rich in Oxygen Vacancies Boost Oxygen Evolution Reaction of Spinel Oxides in Alkaline Media.

As promising oxygen evolution reaction (OER) catalysts, spinel-type oxides face the bottleneck of weak adsorption for oxygen-containing intermediates, so it is challenging to make a further breakthrough in remarkably lowering the OER overpotential. In this study, a novel strategy is proposed to substantially enhance the OER activity of spinel oxides based on amorphous/crystalline phases mixed spinel FeNi2O4 nanosheets array, enriched with oxygen vacancies, in situ grown on a nickel foam (NF). This unique architecture is achieved through a one-step millisecond laser direct writing method. The presence of amorphous phases with abundant oxygen vacancies significantly enhances the adsorption of oxygen-containing intermediates and changes the rate-determining step from OH*→O* to O*→OOH*, which greatly reduces the thermodynamic energy barrier. Moreover, the crystalline phase interweaving with amorphous domains serves as a conductive shortcut to facilitate rapid electron transfer from active sites in the amorphous domain to NF, guaranteeing fast OER kinetics. Such an anodic electrode exhibits a nearly ten fold enhancement in OER intrinsic activity compared to the pristine counterpart. Remarkably, it demonstrates record-low overpotentials of 246 and 315 mV at 50 and 500 mA cm-2 in 1 m KOH with superior long-term stability, outperforming other NiFe-based spinel oxides catalysts.

In Situ Constructed Spinel Layer Stabilized Upcycled LiCoO2 for High Performance Lithium-Ion Batteries.

With ever-increasing requirements for cathodes in the lithium-ion batteries market, an efficiency and eco-friendly upcycling regeneration strategy is imperative to meet the demand for high-performance cathode materials. Herein, a facile, direct and upcycling regeneration strategy is proposed to restore the failed LiCoO2 and enhance the stability at 4.6 V. Double effects combination of relithiation and outside surface reconstruction are simultaneously achieved via a facile solid-phase sintering method. The evolution process of the Li-supplement and grain-recrystallization is systematically investigated, and the high performance of the upcycled materials at high voltage is comprehensively demonstrated. Thanks to the favorable spinel LiCoxMn2-xO4 surface coating, the upcycled sample displays outstanding electrochemical performance, superior to the pristine cathode materials. Notably, the 1% surface-coated LiCoO2 achieves a high discharge-specific capacity of 207.9 mA h g-1 at 0.1 C and delivers excellent cyclability with 77.0% capacity retention after 300 cycles. Significantly, this in situ created spinel coating layer can be potentially utilized for recycling spent LiCoO2, thus providing a viable, promising recycling strategy insights into the upcycling of degraded cathodes.

Unraveling the Impact of Oxygen Vacancy on Electrochemical Valorization of Polyester Over Spinel Oxides.

Electrochemical upcycling of end-of-life polyethylene terephthalate (PET) using renewable electricity offers a route to generate valuable chemicals while processing plastic wastes. However, it remains a huge challenge to design an electrocatalyst with reliable structure-property relationships for PET valorization. Herein, spinel Co3O4 with rich oxygen vacancies for improved activity toward formic acid (FA) production from PET hydrolysate is reported. Experimental investigations combined with theoretical calculations reveal that incorporation of VO into Co3O4 not only promotes the generation of reactive hydroxyl species (OH*) species at adjacent tetrahedral Co2+ (Co2+ Td), but also induces an electronic structure transition from octahedral Co3+ (Co3+ Oh) to octahedral Co2+ (Co2+ Oh), which typically functions as highly-active catalytic sites for ethylene glycol (EG) chemisorption. Moreover, the enlarged Co-O covalency induced by VO facilitates the electron transfer from EG* to OH* via Co2+ Oh-O-Co2+ Td interaction and the following C─C bond cleavage via direct oxidation with a glyoxal intermediate pathway. As a result, the VO-Co3O4 catalyst exhibits a high half-cell activity for EG oxidation, with a Faradaic efficiency (91%) and productivity (1.02 mmol cm-2 h-1) of FA. Lastly, it is demonstrated that hundred gram-scale formate crystals can be produced from the real-world PET bottles via two-electrode electroreforming, with a yield of 82%.