A comprehensive review of Co3O4 nanostructures in cancer: Synthesis, characterization, reactive oxygen species mechanisms, and therapeutic applications.

Nanotechnology involves creating, analyzing, and using tiny materials. Cobalt oxide nanoparticles (Co3O4 NPs) have several medicinal uses due to their unique antifungal, antibacterial, antioxidant, anticancer, larvicidal, anticholinergic, antileishmanial, wound healing, and antidiabetic capabilities. Cobalt oxide nanoparticles (Co3O4 NPs) with attractive magnetic properties have found widespread use in biomedical applications, including magnetic resonance imaging, magnetic hyperthermia, and magnetic targeting. The high surface area of Co3O4 leads to unique electrical, optical, catalytic, and magnetic properties, which make it a promising candidate for biomedical bases. Additionally, cobalt nanoparticles with various oxidation states (i.e., Co2+, Co3+, and Co4+) are beneficial in numerous utilizations. Co3O4 nanoparticles as a catalyzer accelerate the conversion rate of hydrogen peroxide (H2O2) to harmful hydroxyl radicals (•OH), which destroy tumor cells. However, it is also possible to enhance the generation of reactive oxygen species (ROS) and successfully treat cancer by combining these nanoparticles with drugs or other nanoparticles. This review summarizes the past concepts and discusses the present state and development of using Co3O4 NPs in cancer treatments by ROS generation. This review emphasizes the advances and current patterns in ROS generation, remediation, and some different cancer treatments using Co3O4 nanoparticles in the human body. It also discusses synthesis techniques, structure, morphological, optical, and magnetic properties of Co3O4 NPs.

Chemiluminescence detection of kanamycin by DNA aptamer regulating peroxidase-like activity of Co3O4 nanoparticles.

Kanamycin (KAN) is widely used as a growth hormone analog and an antibacterial agent. However, abuse of this substance has resulted in the accumulation of excessive residue levels in foods of animal origin, which presents a significant risk to human health. A chemiluminescent aptasensor was constructed for the rapid quantitative detection of KAN by combining the properties of Co3O4 nanoparticles (Co3O4 NPs) nanozyme activity and DNA aptamer with high specificity. The DNA aptamer/Co3O4 NPs nanozyme regulated the chemiluminescence signal by exploiting the chemiluminescent properties of luminol oxidation by H2O2. Specific binding of KAN to the aptamer led to the formation of a steric hindrance block in the solution, which inhibited the activity of nanozyme and reduced signal intensity. The degree of signal reduction is related to the concentration of KAN. Under optimal conditions, there was good linearity between KAN concentration and chemiluminescence signal intensity in the range of 0.5-8.0 µΜ, with a detection limit of 0.26 µΜ. The detection system performed well in the presence of competing antibiotics and was virtually unaffected. The method was also suitable for the detection of KAN in milk samples with sample recoveries of 97.8%-99.1%. The chemiluminescence sensor has the advantages of low cost, specificity, and sensitivity, and does not require an external light source or modification of the nucleic acid aptamer which makes it a promising candidate for applications in the field of food detection.

Simplified synthesis and identification of novel nanostructures consisting of cobalt borate and cobalt oxide for crystal violet dye removal from aquatic environments.

Crystal violet dye poses significant health risks to humans, including carcinogenic and mutagenic effects, as well as environmental hazards due to its persistence and toxicity in aquatic ecosystems. This study focuses on the efficient removal of crystal violet dye from aqueous media using novel Co3O4/Co3(BO3)2 nanostructures synthesized via the Pechini sol-gel approach. The nanostructures, which were abbreviated to EN600 and EN800, were fabricated at calcination temperatures of 600 and 800 °C, respectively. X-ray diffraction (XRD) analysis revealed that the synthesized samples have a cubic Co3O4 phase and an orthorhombic Co3(BO3)2 phase, with mean crystal sizes of 43.82 nm and 52.93 nm for EN600 and EN800 samples, respectively. The Brunauer-Emmett-Teller (BET) surface areas of EN600 and EN800 samples were 65.80 and 43.76 m2/g, respectively, indicating a significant surface area available for adsorption. Optimal removal of crystal violet dye was achieved at a temperature of 298 K, a contact time of 70 min, and a pH of 10. The maximum adsorption capacities were found to be 284.09 mg/g for EN600 and 256.41 mg/g for EN800, which are notably higher compared to many conventional adsorbents. The adsorption process followed the pseudo-second-order kinetic model and fitted well with the Langmuir isotherm. The adsorption was exothermic, spontaneous, and physical in nature. Moreover, the adsorbents exhibited excellent reusability, retaining high efficiency after multiple regeneration cycles using 6 mol/L hydrochloric acid. These findings highlight the potential of these Co3O4/Co3(BO3)2 nanostructures as effective and sustainable materials for water purification applications.

Boosting Electrochemical Nitrate Reduction to Ammonia by Fe Doped CuO/Co3O4 Nanosheet/Nanowire Heterostructures.

The electrochemical nitrate reduction reaction (NO3-RR) is a novel green method for ammonia synthesis. The development of outstanding NO3-RR performance is based on reasonable catalyst. Metal oxides have garnered significant attention due to their exceptional electrical conductivity and catalytic properties. Doping serves as an effective strategy for enhancing catalyst performance due to its ability to change the electron cloud distribution and energy levels. In this study, we develop a heterojunction catalyst Fe doped copper oxide nanosheet and cobalt tetroxide nanowire growing on carbon cloth simultaneously (Fe-CuO@Co3O4/CC) via hydrothermal method. The well-designed Fe-CuO@Co3O4/CC has excellent NH3 yield (470.9 µmol h-1 cm-2) and Faraday efficiency (FE: 84.4%) at -1.2 V versus reversible hydrogen electrode (vs. RHE). The heterostructure increases the specific surface area of the catalyst, and the possibility of contact between the catalyst and NO3- ions, enhances the catalytic efficiency. In addition, the catalyst has excellent stability and can stably carry out the electrocatalytic nitrate reduction reaction (NO3-RR), which provides a way for further research on the high-efficiency reduction of nitrate.

Efficient ofloxacin degradation via peroxymonosulfate activation using an S-scheme MoS2/Co3O4 heterojunction composite under visible light: Performance and mechanistic insights.

Sulfate-radical-mediated photocatalysis technology peroxymonosulfate (PMS) activation via visible light irradiation shows great promise for water treatment applications. However, its effectiveness largely depends on the bifunctional performance of photocatalysis and PMS activation provided by the catalysts. In this study, we successfully synthesized a novel S-scheme MoS2/Co3O4 (MC) heterojunction composite by a hydrothermal method and employed it for the first time to activate PMS for ofloxacin (OFX) degradation under visible light irradiation. The MC-5/PMS/Vis system achieved an impressive 85.11% OFX degradation efficiency within 1 min and complete OFX removal within 15 min under optimal conditions, with an apparent first-order kinetics rate constant of 0.429 min-1. Reactive species trapping experiments and electron spin resonance analysis identified 1O2, h+, and •O2- as the primary active species responsible for OFX degradation. Photoelectrochemical analyses and density functional theory calculations indicated the formation of a built-in electric field between MoS2 and Co3O4, which enhanced the separation and migration of photoinduced carriers. Additionally, the Co-Mo interaction further increased the yield of dominant reactive species, thereby boosting photocatalytic activity. This work underscores the potential of visible-light-assisted PMS-mediated photocatalysis using Co3O4-based catalysts for effective pollutant control.

Modulating Silver Performance in Electrocatalytic Oxidation of HCHO via SMSI between Ag-Co3O4 Interfaces.

The replacement of oxygen evolution reactions with organic molecule oxidation reactions to enable energy-efficient hydrogen production has been a subject of interest. However, further reducing reaction energy consumption and releasing hydrogen from organic molecules continue to pose significant challenges. Herein, a strategy is proposed to produce hydrogen and formic acid from formaldehyde using Ag/Co3O4 interface catalysts at the anode. The key to improving the performance of Ag-based catalysts for formaldehyde oxidation lies in the strong SMSI achieved through the well-designed "spontaneous redox reaction" between Ag and Co3O4 precursors. Nano-sized Ag particles are uniformly dispersed on Co3O4 nanosheets, and electron-deficient Agδ+ are formed by the SMSI between Ag and Co3O4. Ag/Co3O4 demonstrates exceptional formaldehyde oxidation activity at low potentials of 0.32 V versus RHE and 0.65 V versus RHE, achieving current densities of 10 and 100 mA cm-2, respectively. The electrolyzer "Ag/Co3O4||20% Pt/C" achieves over 195% hydrogen efficiency and over 98% formic acid selectivity, maintaining stable operation for 60 hours. This work not only presents a novel approach to precisely modulate Ag particle size and interface electronic structure via SMSI, but also provides a promising approach to efficient and energy-saving hydrogen production and the transformation of harmful formaldehyde.

Electrochemical treatment of simulated wastewater containing nitroaromatic compound with cobalt-titanium electrode.

The Co3O4-Ti electrodes were successfully prepared via calcination method to degrade nitrogen-containing (TNP) simulate wastewater in this reaserch. SEM and EDS were employed to analyze the morphology and element composition on Co3O4-Ti electrode, revealing the successful load of cobalt element. Then the electrochemical performance was evaluated by CV and indicated a better redox performance of electrode. Furthermore, five factors as processing time (A), electrolyte concentration (B), pH (C), initial concentration of TNP (D), and current density (E) were systematic studied in electrical treatment process. The removal rate of TN could be 77%. After the optimization work by RSM, the removal rate of TN raised up to 81% with the condition as: A of 180 min, B of 0.05 M, C of 3, D of 400 mg L-1, and E of 20 mA cm-2. The sequence of significants is: C > D > A > E > B. Mechanism analysis revealed that the entire process could be divided into two stages. In the first stage, organic nitrogen compounds were converted into inorganic nitrogen species, such as NO3-N. The oxidation and reduction would react owing to the generating of ·OH at second stage in order to turn the NO3-N into NO2-N, NH4-N or N2. The activation of ·OH on the surface of Co3O4-Ti electrode possesses the exothermic nature with transition theory. The energy calculation of 1.168 eV indicated these reactions could occur spontaneously.

2D/2D Co3O4/BiOCl nanocomposite with enhanced antibacterial activity under full spectrum: Synergism of mesoporous structure, photothermal effect and photocatalytic reactive oxygen species.

The overuse of antibiotics has caused the emergence of drug-resistant bacteria and even superbugs, which makes it imperative to develop promising antibiotic-free alternatives. Herein, a multimodal antibacterial nanoplatform of two dimensional/two dimensional (2D/2D) mesoporous Co3O4/BiOCl nanocomposite is constructed, which possesses the effect of "kill three birds with one stone": (1) the use of mesoporous Co3O4 can enlarge the surface area of the nanocomposite and promote the adsorption of bacteria; (2) Co3O4 displays remarkable full-spectrum absorption and photo-induced self-heating effect, which can raise the temperature of Co3O4/BiOCl and help to kill bacteria; (3) the p-type Co3O4 and n-type BiOCl form a p-n heterojunction, which promotes the separation of photoelectrons and holes, thus producing more reactive oxygen species (ROS) for killing bacteria. The synergism of mesoporous structure, photothermal effect and photocatalytic ROS makes the developed Co3O4/BiOCl a promising antibacterial material, which shows outstanding antibacterial activity with an inhibition rate of nearly 100 % against Escherichia coli (E. coli) within 8 min. This work provides inspiration for designing multimodal synergistic nanoplatform for antibacterial applications.

Bias-free glucose/O2 bio-photoelectrochemical system for multi-energy conversion and phenolic pollutant degradation.

Developing a multi-functional green energy device that propels sustainable energy development and concurrently purifies environmental pollutants offers an irresistibly compelling vision for a cleaner future. Herein, we reported a bias-free glucose/O2 bio-photoelectrochemical system (BPECS) for both energy conversion and phenolic pollutants degradation. Coupling a glucose dehydrogenase (GDH) modified self-assembled meso-tetrakis (4-carboxyphenyl)-porphyrin (SA-TCPP)-sensitized TiO2 biophotoanode for glucose oxidation and nitrogen/oxygen doped cobalt single-atom catalyst (CoNOC) cathode for two-electron oxygen reduction, both solar and biochemical energies were converted into electric power in BPECS with a maximum power density of 296.98 µW cm-2 (0.49 V). Working in synergy with horseradish peroxidase (HRP) biocatalysis, the cathode-generated H2O2, a by-product, is effectively redeployed for degrading phenol, attaining an impressive degradation efficiency of approximately 100% within 60 min. Additionally, aiming to scale up this ingenious BPECS approach, peroxidase-mimicking Co3O4 nanozyme were engineered as a substitute for natural HRP. Remarkably, these nanozyme demonstrated a comparable degradation efficiency, achieving the same result in 90 min. In this work, our results demonstrate that this bias-free glucose/O2 BPECS model marks a significant step forward in integrating renewable energy harvesting with environmental remediation, but also opens new avenues for the versatile application of nanozymes.

Asymmetric defective sites-mediated high-valent cobalt-oxo species in self-suspension aerogel platform for efficient peroxymonosulfate activation.

The main pressing problems should be solved for heterogeneous catalysts in activation of peroxymonosulfate (PMS) are sluggish mass transfer kinetics and low intrinsic activity. Here, oxygen vacancies (Vo)-rich of Co3O4 nanosheets were anchored on the superficies of spirulina-based reduced graphene oxide-konjac glucomannan (KGM) aerogel (R-Co3O4-x/SRGA). The porous structure and superhydrophilicity conferred by KGM maximized the diffusion and transport of reactant. More interestingly, R-Co3O4-x/SRGA came true self-suspension rather than conventional self-floating without the aid of external force, maximizing space utilization and facilitating catalysts recovery. Anchored R-Co3O4-x nanosheets acted as "engines" to drive the reaction. Density functional theory (DFT) manifested Vo was capable of breaking the symmetry of the electronic structure of Co3O4. The formation of asymmetric active sites (Vo) was revealed to modulate the d-band center, enhanced affinity for PMS, and promoted evolution of high-valent cobalt-oxo (Co(IV)=O) species. R-Co3O4-x/SRGA achieved complete removal of sulfamethoxazole (SMX) within 12 min. Furthermore, R-Co3O4-x/SRGA demonstrated exceptional stability in the presence of various environmental interference factors and continuous flow device. This insightful work cleverly integrates the macroscopic design of structure, and the microscopic regulation of active sites is expected to open up new opportunities for the development of water treatment.

Co3O4/CuO@C catalyst based on cobalt-doped HKUST-1 as an efficient peroxymonosulfate activator for pendimethalin degradation: Catalysis and mechanism.

Pendimethalin (PM) is an organic pollutant (herbicide), and systematic studies on PM degradation are scarce. The efficient degradation of PM in water remains a challenge that requires to be addressed. Herein, for the first time, elemental Co was doped into HKUST-1 using a solvothermal method to generate Co3O4/CuO@C via pyrolysis. The as-prepared catalyst was used to activate peroxymonosulfate (PMS) for PM degradation, obtaining a PM degradation efficiency of 98.2 % after 30 min. The assessment of the effects of various factors on the degradation efficiency revealed that 1O2 dominated PM degradation, whereas the contribution of SO4•- was negligible. Although 3Co3O4/CuO@C exhibited a good degradation performance against other organic pollutants, its degradation performance in real water was poor. The carbon layer reduced metal-ion leaching (Co and Cu), and the synergistic interactions between Co3O4 and CuO promoted PMS activation. The roles of the components of 3Co3O4/CuO@C in PM degradation by activated PMS were investigated in the presence of CoIV and Co-OOSO3-. Two possible PM degradation pathways were systematically proposed, and the toxicity of the intermediates was analyzed. Finally, a mechanism for PM degradation by 3Co3O4/CuO@C-activated PMS was proposed.

Efficient mixed-potential acetone sensor with yttria-stabilized zirconia and porous Co3O4 nanofoam sensing electrode for hazardous gas monitoring and breath analysis.

For hazardous gas monitoring and non-invasive diagnosis of diabetes using breath analysis, porous foams assembled by Co3O4 nanoparticles were designed as sensing electrode materials to fabricate efficient yttria-stabilized zirconia (YSZ)-based acetone sensors. The sensitivity of the sensors was improved by varying the sintering temperature to regulate the morphology. Compared to other materials sintered at different temperatures, the porous Co3O4 nanofoams sintered at 800 °C exhibited the highest electrochemical catalytic activity during the electrochemical test. The response of the corresponding Co3O4-based sensor to 10 ppm acetone was -77.2 mV and it exhibited fast response and recovery times. Moreover, the fabricated sensor achieved a low detection limit of 0.05 ppm and a high sensitivity of -56 mV/decade in the acetone concentration range of 1-20 ppm. The sensor also exhibited excellent repeatability, acceptable selectivity, good O2/humidity resistance, and long-term stability during continuous measurements for over 30 days. Moreover, the fabricated sensor was used to determine the acetone concentration in the exhaled breaths of patients with diabetic ketosis. The results indicated that it could distinguish between healthy individuals and patients with diabetic ketosis, thereby proving its abilities to diagnose and monitor diabetic ketosis. Based on its excellent sensitivity and exhaled breath measurement results, the developed sensor has broad application prospects.

Exploring the Impact of Oxygen Vacances in Co/Pr-CeO2 Catalysts on H2 Production via the Water-Gas Shift Reaction.

In this study, we utilized various Pr-doped CeO2 catalysts (Pr=5, 10, 20, and 30 wt.%) as a support medium for the dispersion of cobalt (Co) nanoparticles, aiming to investigate the impact of oxygen vacancies on the water-gas shift (WGS) reaction. Different characterization techniques were employed to understand the insights into the structure-activity relationship governing the performance of Pr doped ceria supported Co catalysts towards WGS reaction. Our findings reveal that Co/Pr-CeO2 catalysts at optimum Pr loading (10 wt.%) exhibit a superior CO conversion (88%) facilitated by the presence of more oxygen vacancies induced by Pr doping into the CeO2 lattice, as opposed to the performance of the pure Co/CeO2 catalytic system. It was also found that the highest activity was obtained at increased intrinsic oxygen vacancies and strong synergy between Co and Pr/CeO2 support, fostering more favorable CO activation at the interfacial sites, thus accounting for the observed enhanced activity.

Application of N-doped NiCo2O4/NiO/Co3O4composites rich in oxygen vacancies in electromagnetic wave absorption.

In this work, N-doped and oxygen vacancy-rich NiCo2O4/NiO/Co3O4composites are synthesized by the direct calcination method. Noticeably, by changing the additive concentrations of urea dissolved in DMF (N-N dimethylformamide), the electromagnetic wave (EMW) absorption abilities of NiCo2O4/NiO/Co3O4composite effectively. A maximum reflection loss (RLmax) value at 12.94 GHz for a 2.8 mm thick sheet is -29.76 dB, while its effective absorption bandwidth (RL < -10 dB) reaches 4.21 GHz. In-depth research of possible mechanisms of EMW absorption enhancement. Owing to its simple preparation method and superb EMW absorption properties, the NiCo2O4/NiO/Co3O4composites have a chance to be suitable candidates for high-property EMW absorbers.

Architectural Decoration of Bioleached NiFeP Surfaces by Co3O4 Flowers for Efficient Electrocatalytic Hydrogen Generation.

In the quest for sustainable hydrogen production via water electrolysis, the development of high-performance, noble-metal-free catalytic systems is highly desired. Herein, we proposed an innovative strategy for the development of an electrocatalyst by refining the surface characteristics of a NiFeP alloy through microbiological techniques and subsequent enrichment of active sites by tailoring 3D hierarchical flower-like structures with intact and interconnected two-dimensional (2D) Co3O4. The resultant 3D Co3O4@NiFeP-5/24h has a porous structure comprised of intercrossed nanoparticles covering the entirety of the catalytic surface. This design ensures comprehensive electrolyte ion penetration and facilitates the release of gas bubbles while reducing bubble adhesion rates. Remarkably, the Co3O4@NiFeP-5/24h electrode demonstrates superior hydrogen evolution (HER) performance in an alkaline medium, characterized by its high stability, low overpotential (106 mV at a current density of 10 mA cm-2), and reduced Tafel slope (98 mV dec-1). Besides, the minimized interfacial contact resistance among the phases of electrode and electrolyte emphasizes the high HER performance of the 3D Co3O4@NiFeP-5/24h electrode. The innovative design and fabrication strategy employed herein holds significant potential for advancing the field of water-splitting electrocatalysis, offering a promising path toward the rational design and development of noble-metal-free electrocatalysts.

The fate and impact of Co3O4 nanoparticles in the soil environment: Observing the dose effect of nanoparticles on soybeans.

The widespread presence and distribution of metal-based nanoparticles (NPs) in soil is threatening crop growth and food security. However, little is known about the fate of Co3O4 NPs in the soil-soybean system and their phytotoxicity. The study demonstrated the effects of Co3O4 NPs on soybean growth and yield in soil after 60 days and 140 days, and compared them with the phytotoxic effects of Co2+. The results showed that Co3O4 NPs (10-500 mg/kg) had no significant toxic effect on soybeans. Soil available Co content was significantly increased under 500 mg/kg Co3O4 NPs treatment. Compared with Co2+, Co3O4 NPs mainly accumulated in roots and had limited transport to the shoots, which was related to the particle size, surface charge and chemical stability of Co3O4 NPs. The significant accumulation of Co3O4 NPs in roots further led to a significant decrease in root antioxidant enzyme activity and changes in functional gene expression. Co3O4 NPs reduced soybean yield after 140 days, but interestingly, at specific doses, it increased grain nutrients (Fe content increased by 17.38% at 100 mg/kg, soluble protein and vitamin E increased by 14.34% and 16.81% at 10 mg/kg). Target hazard quotient (THQ) assessment results showed that consuming soybean seeds exposed to Co3O4 NPs (≥100 mg/kg) and Co2+ (≥10 mg/kg) would pose potential health risks. Generally, Co3O4 NPs could exist stably in the environment and had lower environmental risks than Co2+. These results help to better understand the environmental behavior and plant effect mechanisms of Co3O4 NPs in soil-plant systems.

Enhancing Oxygen Activation Ability by Composite Interface Construction over a 2D Co3O4-Based Monolithic Catalyst for Toluene Oxidation.

Developing robust metal-based monolithic catalysts with efficient oxygen activation capacity is crucial for thermal catalytic treatment of volatile organic compound (VOC) pollution. Two-dimensional (2D) metal oxides are alternative thermal catalysts, but their traditional loading strategies on carriers still face challenges in practical applications. Herein, we propose a novel in situ molten salt-loading strategy that synchronously enables the construction of 2D Co3O4 and its growth on Fe foam for the first time to yield a unique monolithic catalyst named Co3O4/Fe-S. Compared to the Co3O4 nanocube-loaded Fe foam, Co3O4/Fe-S exhibits a significantly improved catalytic performance with a temperature reduction of 44 °C at 90% toluene conversion. Aberration-corrected scanning transmission electron microscopy and theoretical calculation suggest that Co3O4/Fe-S possesses abundant 2D Co3O4/Fe3O4 composite interfaces, which promote the construction of active sites (oxygen vacancy and Co3+) to boost oxygen activation and toluene chemisorption, thereby accelerating the transformation of reaction intermediates through Langmuir-Hinshelwood (L-H) and Mars-van Krevelen (MvK) mechanisms. Moreover, the growth mechanism reveals that 2D Co3O4/Fe3O4 composite interfaces are generated in situ in molten salt, inducing the growth of 2D Co3O4 onto the surface lattice of 2D Fe3O4. This study provides new insights into enhancing oxygen activation and opens an unprecedented avenue in preparing efficient monolithic catalysts for VOC oxidation.

Efficient Electroreduction of Low Nitrate Concentration via Nitrate Self-Enrichment and Active Hydrogen Inducement on the Ce(IV)-Co3O4 Cathode.

Low concentrations of nitrate (NO3-) widely exist in wastewater, post-treated wastewater, and natural environments; its further disposal is a challenge but meaningful for its discharge goals. Electroreduction of NO3- is a promising method that allows to eliminate NO3- and even generate higher-value NH3. However, the massive side reaction of hydrogen evolution has raised great obstacles in the electroreduction of low concentrations of NO3-. Herein, we present an efficient electroreduction method for low or even ultralow concentrations of NO3- via NO3- self-enrichment and active hydrogen (H*) inducement on the Ce(IV)-Co3O4 cathode. The key mechanism is that the strong oxytropism of Ce(IV) in Co3O4 resulted in two changes in structures, including loose nanoporous structures with copious dual adsorption sites of Ce-Co showing strong self-enrichment of NO3- and abundant oxygen vacancies (Ovs) inducing substantial H*. Ultimately, the bifunctional role synergistically promoted the selective conversion of NH3 rather than H2. As a result, Ce(IV)-Co3O4 demonstrated a NO3- self-enrichment with a 4.3-fold up-adsorption, a 7.5-fold enhancement of NH3 Faradic efficiency, and a 93.1% diminution of energy consumption when compared to Co3O4, substantially exceeding other reported electroreduction cathodes for NO3- concentrations lower than 100 mg·L-1. This work provides an effective treatment method for low or even ultralow concentrations of NO3-.

Facet-Dependent Evolution of Active Components on Spinel Co3O4 for Electrochemical Ammonia Synthesis.

Spinel cobalt oxides (Co3O4) have emerged as a promising class of catalysts for the electrochemical nitrate reduction reaction (eNO3RR) to ammonia, offering advantages such as low cost, high activity, and selectivity. However, the specific role of crystallographic facets in determining the catalysts' performance remains elusive, impeding the development of efficient catalysts. In this study, we have synthesized various Co3O4 nanostructures with exposed facets of {100}, {111}, {110}, and {112}, aiming to investigate the dependence of the eNO3RR activity on the crystallographic facets. Among the catalysts tested, Co3O4 {111} shows the best performance, achieving an ammonia Faradaic efficiency of 99.1 ± 1.8% with a yield rate of 35.2 ± 0.6 mg h-1 cm-2 at -0.6 V vs RHE. Experimental and theoretical results reveal a transformation process in which the active phases evolve from Co3O4 to Co3O4-x with oxygen vacancy (Ov), followed by a Co3O4-x-Ov/Co(OH)2 hybrid, and finally Co(OH)2. This process is observed for all facets, but the formation of Ov and Co(OH)2 is the most rapid on the (111) surface. The presence of Ov significantly reduces the free energy of the *NH2 intermediate formation from 1.81 to -0.53 eV, and plentiful active sites on the densely reconstructed Co(OH)2 make Co3O4 {111} an ideal catalyst for ammonia synthesis via eNO3RR. This work provides insights into the understanding of the realistic active components, offers a strategy for developing highly efficient Co-based spinel catalysts for ammonia synthesis through tuning the exposed facets, and helps further advance the design and optimization of catalysts in the field of eNO3RR.

Engineering In-Co3O4/H-SSZ-39(OA) Catalyst for CH4-SCR of NOx: Mild Oxalic Acid (OA) Leaching and Co3O4 Modification.

Zeolite-based catalysts efficiently catalyze the selective catalytic reduction of NOx with methane (CH4-SCR) for the environmentally friendly removal of nitrogen oxides, but suffer severe deactivation in high-temperature SO2- and H2O-containing flue gas. In this work, SSZ-39 zeolite (AEI topology) with high hydrothermal stability is reported for preparing CH4-SCR catalysts. Mild acid leaching with oxalic acid (OA) not only modulates the Si/Al ratio of commercial SSZ-39 to a suitable value, but also removes some extra-framework Al atoms, introducing a small number of mesopores into the zeolite that alleviate diffusion limitation. Additional Co3O4 modification during indium exchange further enhances the catalytic activity of the resulting In-Co3O4/H-SSZ-39(OA). The optimized sample exhibits remarkable performance in CH4-SCR under a gas hourly space velocity (GHSV) of 24,000 h-1 and in the presence of 5 vol% H2O. Even under harsh SO2- and H2O-containing high-temperature conditions, it shows satisfactory stability. Catalysts containing Co3O4 components demonstrate much higher CH4 conversion. The strong mutual interaction between Co3O4 and Brønsted acid sites, confirmed by the temperature-programmed desorption of NO (NO-TPD), enables more stable NxOy species to be retained in In-Co3O4/H-SSZ-39(OA) to supply further reactions at high temperatures.