Energy & Environmental Materials
·
2024
·
IF 13
Li Zhang,Peiyue Jin,Ze Wu,Bo Zhou,Junchang Jiang,Aomeng Deng,Qiuyue Li,Tanveer Hussain,Yiqiong Zhang,Hanwen Liu,Shuangyin Wang
The electrochemical coupling of biomass oxidation and nitrogen conversion presents a potential strategy for high value-added chemicals and nitrogen cycling. Herein, in this work, CuO/Co 3 O 4 with heterogeneous interface is successfully constructed as a bifunctional catalyst for the electrooxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid and the electroreduction of nitrate to ammonia (NH 3 ). The open-circuit potential spontaneous experiment shows that more 5-hydroxymethylfurfural molecules are adsorbed in the Helmholtz layer of the CuO/Co 3 O 4 composite, which certifies that the CuO/Co 3 O 4 heterostructure is conducive to the kinetic adsorption of 5-hydroxymethylfurfural. In situ electrochemical impedance spectroscopy further shows that CuO/Co 3 O 4 has faster reaction kinetics and lower reaction potential in oxygen evolution reaction and 5-hydroxymethylfurfural electrocatalytic oxidation. Moreover, CuO/Co 3 O 4 also has a good reduction effect on NO 3 − $$ {\mathrm{NO}}_3^{-} $$ . The ex-situ Raman spectroscopy shows that under the reduction potential, the metal oxide is reduced, and the generated Cu 2 O can be used as a new active site for the reaction to promote the electrocatalytic conversion of NO 3 − $$ {\mathrm{NO}}_3^{-} $$ to NH 3 synthesis. This work provides valuable guidance for the synthesis of value-added chemicals by 5-hydroxymethylfurfural electrocatalytic oxidation coupled with NO 3 − $$ {\mathrm{NO}}_3^{-} $$ while efficiently producing NH 3 .
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高影响因子
FUEL
·
2025
·
IF 7.5
Guoyang Zhao,Yafei Guo,Pu Huang,Zhouzhou Zhang,Chuanwen Zhao
Developing highly efficient and robust catalysts for low-temperature CO oxidation is essential for CO abatement in sintering flue gas. CuO-Co 3 O 4 catalysts incorporated with transition metal oxides (TMOs) of CeO 2 , ZrO 2 , NiO or Fe 2 O 3 were synthesized using the sol–gel method. The crystalline structure, morphology, electronic structure, surface active sites and redox properties of the composite catalysts were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), CO temperature-programmed desorption (CO-TPD), H 2 temperature-programmed reduction (H 2 -TPR), and O 2 temperature-programmed oxidation (O 2 -TPO). The influence of incorporating TMO on CO oxidation performance of the composite catalysts was thoroughly investigated. Results indicated that incorporating CeO 2 and ZrO 2 enhanced the CO oxidation activity of CuO-Co 3 O 4 significantly, achieving notably low T 100 temperatures of 134 °C and 150°C. The desired CuO-Co 3 O 4 -CeO 2 and CuO-Co 3 O 4 -ZrO 2 composite catalysts also showed outstanding CO oxidation kinetics performance with low activation energies of 25.36 and 26.41 kJ/mol, and remarkable time-on-stream stability, sustaining a near 100 % CO conversion rate for up to 25 h. The superior CO oxidation performance was associated with the smaller crystallite sizes, uniformly dispersed active sites, abundant oxygen vacancies, and enhanced redox properties, all of which stemmed from the strengthened interfacial interactions among the metal oxides upon CeO 2 and ZrO 2 incorporation. These findings offer valuable insights into the structure–property-activity relationships of the CuO-Co 3 O 4 -TMO composite catalysts, positioning the CuO-Co 3 O 4 -CeO 2 and CuO-Co 3 O 4 -ZrO 2 samples as promising candidates for low-temperature CO oxidation in sintering flue gas treatment.
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APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Kexin Tian,Ye Liu,Yating Fu,Yi Ren,Chuanshu He,Zhaokun Xiong,Heng Zhang,Yang Liu,Jianping Zou,Jing Zhang,Bo Lai
A novel surface oxidation-dominated heterogeneous catalytic ozonation (HCO) process was developed to overcome matrix-induced scavenging limitations. By fabricating CuO-Co 3 O 4 heterojunction as catalyst, surface adsorbed hydroxyl radical (•OH ad ) and surface atomic oxygen ( ⁎ O ad ) emerge as primary reactive oxygen species (ROS) from ozone decomposition. The engineered catalyst achieves 4.3-fold and 1.9-fold higher oxalic acid degradation efficiency than CuO and Co 3 O 4 , respectively, accompanied by broad-spectrum mineralization for refractory pollutants and robust Cl⁻ resistance with verification in actual hypersaline industrial wastewater treatment. Combined characterization and theoretical calculations reveal that heterojunction formation increases Lewis acid sites and induces directional electron transfer from CuO to Co 3 O 4 , thereby lowering ozone activation barriers and accelerating surface-bound ROS generation, wherein O 3 is preferentially decomposed into •OH ad and ⁎ O ad at Co sites but only •OH ad at Cu sites. Collectively, this study advances a surface-bound ROS mediated catalytic ozonation paradigm with superior matrix resistance, enabling broader industrial deployment of HCO.
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CHINESE JOURNAL OF CHEMICAL ENGINEERING
·
2021
·
IF 3.171
Yingmeng Zhang,Luting Liu,Qingwei Deng,Wanlin Wu,Yongliang Li,Xiangzhong Ren,Peixin Zhang,Lingna Sun
Hybrid CuO-Co 3 O 4 nanosphere building blocks have been embedded between the layered nanosheets of reduced graphene oxides with a three dimensional (3D) hybrid architecture (CuO-Co 3 O 4 -RGO), which are successfully applied as enhanced anodes for lithium-ion batteries (LIBs). The CuO-Co 3 O 4 -RGO sandwiched nanostructures exhibit a reversible capacity of ~847 mA·h·g −1 after 200 cycles’ cycling at 100 mA·g −1 with a capacity retention of 79%. The CuO-Co 3 O 4 -RGO compounds show superior electrochemical properties than the comparative CuO-Co 3 O 4 , Co 3 O 4 and CuO anodes, which may be ascribed to the following reasons: the hybridizing multicomponent can probably give the complementary advantages; the mutual benefit of uniformly distributing nanospheres across the layered RGO nanosheets can avoid the agglomeration of both the RGO nanosheets and the CuO-Co 3 O 4 nanospheres; the 3D storage structure as well as the graphene wrapped composite could enhance the electrical conductivity and reduce volume expansion effect associated with the discharge-charge process.
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高影响因子
Nanomaterials
·
2023
·Vol. 13
·期 24
·3153
·
IF 5.3
Zhenteng Sheng,Hui Zhou,Yuhua Zhang,Jinlin Li,Li Wang
The selective hydrogenation of CO2into high-value chemicals is an effective approach to address environmental issues. Cobalt-based catalysts have significant potential in CO2hydrogenation reaction systems; however, there is a need to control their selectivity better. In this study, copper is introduced onto Co3O4nanosheets using the ion exchange reverse loading method. The unique interaction of these materials significantly alters the selectivity of the cobalt-based catalyst. Results from scanning transmission electron microscopy and scanning electron microscopy indicate that this catalyst enables a more even dispersion of copper species in the Co3O4nanosheets. Temperature-programmed reduction and X-ray photoelectron spectroscopy reveal that the catalyst facilitates the metal–metal interaction between Co and Cu. Temperature-programmed desorption experiments for CO2and H2demonstrate that the close interaction between Co and Cu modifies CO2adsorption, leading to differences in catalytic activity. Moreover, the catalyst effectively suppresses CO2methanation and promotes methanol formation by altering the alkalinity of the catalyst surface and weakening the hydrogen dissociation ability.Keywords:CO2hydrogenation;methanol;cobalt;copper
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PubMed
高影响因子
NEW JOURNAL OF CHEMISTRY
·
2024
·Vol. 48
·期 28
·12535-12543
·
IF 2.7
Bo Sun,Man Li,Lifeng Cheng,Qijian Li,Xiaowen Chen,Shengqi Wang,Wenhua Yan,Lei Wang,Fuxiang Wei,Qingliang Wang
Transition metal oxides (TMOs) have excellent electrochemical properties. However, they are commonly associated with short cycle lives, agglomeration, and lower electrical conductivity. To ameliorate these drawbacks, porous rod-shaped CuO@Co3O4 has been synthesized through calcination with optimized oxidation temperature by using CuCo-MOF-74 as a template. Due to the porous structure, the CuO@Co3O4 electrode significantly increases the contact area with the electrolyte and greatly improves the reaction kinetics. As a result, the CuO@Co3O4 electrode exhibits excellent electrochemical performance with a specific capacitance of 545.5 F g−1 at a current density of 1 A g−1. The capacitance retention at 10 A g−1 was 88.7% after 10 000 cycles. Furthermore, an asymmetric supercapacitor (SC) has been assembled with CuO@Co3O4 as the positive electrode and commercial reduced graphene oxide (RGO) as the negative electrode, and the device has exhibited an energy density of 38.2 W h kg−1 at a power density of 1268.3 W kg−1. Impressively, the capacitance retention remained 83.2% even after 10 000 cycles at a high current density of 10 A g−1. This performance has demonstrated the potential of CuO@Co3O4 as an anode material for SCs.
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CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Yufeng Wu,Shiyang Feng,Kui Yang,Wenjian Yang,Chao Li,Xuejun Cui,Jinxing Ma
Electrochemical ammonia synthesis via nitrate reduction reaction (NO 3 RR) offers a sustainable solution for mitigating nitrate pollution while recovering valuable nitrogen resources. Conventional flow-by/batch systems suffer from slow kinetics and low current efficiency due to a thick boundary layer at the electrode surface, which impairs NO 3 RR activity and selectivity. This study introduces a novel flow-through configuration employing a micron-porous CuO-Co 3 O 4 composite membrane electrode for enhanced NO 3 RR. Computational fluid dynamics simulations revealed a significantly thinner boundary layer (∼10 μm) in the flow-through mode compared to flow-by (>120 μm). Consequently, the flow-through mode exhibited a seven-fold increase in NO 3 RR kinetics, boosting the ammonia Faradaic efficiency (FE) from 7.2 % to 79.8 %. Optimization of the Co 3 O 4 membrane electrode, addressing parameters of Cu/Co loading and pore size, further enhanced performance. This achieved high ammonia selectivity and FE (up to 95.7 % and 88.1 %, respectively) across a broad nitrate concentration range (0.02–1.0 g N L −1 ). Mechanistic investigations, integrating scavenger-quenching experiments, electrochemical analyses, and electron paramagnetic resonance spectroscopy demonstrated that ammonia synthesis primarily followed the dominance of the direct electron transfer (DET) between the flow-through cathode and nitrate/nitrite, while hydrogen species (H*) served an auxiliary function. These results underscore the effectiveness of the flow-through membrane electrode configuration in facilitating efficient electrochemical ammonia synthesis, offering valuable insights for the advancement of electrochemical technologies for pollution control and resource recovery.
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JOURNAL OF HAZARDOUS MATERIALS
·
2019
·
IF 7.65
Wei Li,Yuxin Li,Deyun Zhang,Yeqing Lan,Jing Guo
CuO-Co 3 O 4 @CeO 2 nanoparticles used as a heterogeneous catalyst were prepared via a sol-gel method and characterized by various techniques. For comparison, a series of oxides was investigated for activating peroxymonosulfate (PMS) during the degradation of 2,4-dichlorophenoxyacetic acid (2,4-D). The results indicated that CuO-Co 3 O 4 @CeO 2 exhibited the highest catalytic performance among the catalysts. Complete degradation of 2,4-D (20 mg/L) was realized within 45 min at 1 mM PMS, CuO-Co 3 O 4 @CeO 2 loading of 0.07 g/L, and pH of 6. Recycling experiments confirmed that CuO-Co 3 O 4 @CeO 2 was very stable, and the 2,4-D degradation efficiencies ranged from 100% to 97.5%, decreasing by only 2.5% after the fifth run. The outstanding catalysis of CuO-Co 3 O 4 @CeO 2 resulted from the synergy of cerium, cobalt, and copper. Electron paramagnetic resonance and radical scavenger experiments confirmed the production of SO 4 • − and • OH radicals in the CuO-Co 3 O 4 @CeO 2 /PMS system, which were responsible for efficient decomposition of 2,4-D. Furthermore, the combination of CuO-Co 3 O 4 @CeO 2 andPMS was applied to treat natural water containing 2,4-D, and a high 2,4-D removal rate was also achieved. Based on these results, it was deduced that CuO-Co 3 O 4 @CeO 2 can be utilized as a catalyst to activate PMS and destroy organic contaminants in aqueous solution.
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2017
·
IF 3.582
Haiyan Shen,Dawei Ni,Ping Niu,Yi Zhou,Tianyou Zhai,Ying Ma
Spatially controlled co-loading of both oxidation and reduction cocatalysts on semiconductor photocatalysts has been demonstrated to be favorable for photogenerated charge separation and thus enhanced photocatalytic activity. Herein, we presented a simple ball-milling method to improve photocatalytic H 2 production of TiO 2 by co-loading of oxidation cocatalyst Co 3 O 4 with reduction cocatalyst CuO , wherein the Co 3 O 4 loading amount was significant especially for TiO 2 loaded with sufficient or optimum CuO. In comparison with that on TiO 2 loaded with only CuO, the photocatalytic H 2 production from water over TiO 2 photocatalyst co-loaded with CuO and trace Co 3 O 4 was enhanced by approximately 5.5 times, even though complex spatial control was not adopted. In contrast, remarkable improvement of photocatalytic activity after Co 3 O 4 co-loading was only observed on TiO 2 photocatalysts loaded with less CuO in the presence of methanol. Better separation of photogenerated charges on the surface of dual-cocatalysts modified TiO 2 was further demonstrated by decreased luminescence as well as increased photogenerated electrons and hydroxyl radicals as compared to those loaded with only CuO.
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Catalysts
·
2025
·Vol. 15
·期 6
·538
·
IF 4
Jinlong Wen,Ziying Hu,Hongpeng Jia,Jing Chen,Can-Zhong Lu
The construction of multicomponent transition metal oxide catalysts can effectively increase the surface defects of catalysts, and bring a synergistic effect from different components, thus enhancing the generation of reactive oxygen species and improving the catalytic activity of catalysts for volatile organic compounds (VOCs) oxidation. In this article, CuO/Co3O4catalysts with abundant oxygen vacancies for the degradation of ethyl acetate was prepared by a simple impregnation method. The effect of the ratio of Co/Cu on the redox capacity, oxygen vacancy, active oxygen species and catalytic oxidation activity of ethyl acetate were studied. The 90% conversion and mineralization temperatures of ethyl acetate for the optimal catalyst Co3O4-20Cu are 211 and 214 °C (WHSV = 60,000 mL/(g·h), 1000 ppm ethyl acetate), which also shows good stability and excellent water vapor resistance. Compared with pure Co3O4, the CuO/Co3O4catalysts have more oxygen vacancies, provide more reactive oxygen species, allowing the catalyst better low-temperature reduction. Through in situ DRIFTS study, the intermediates of ethyl acetate decomposition were analyzed, then a possible catalytic oxidation mechanism of ethyl acetate on the Co3O4-20Cu catalyst was proposed. In addition, we prepared a Co3O4-20Cu/cordierite monolithic catalyst on the basis of Co3O4-20Cu, exhibiting a good catalytic activity in degradation of ethyl acetate.
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高影响因子
LANGMUIR
·
2026
·Vol. 42
·期 32
·23767-23775
·
IF 4.4
Luo Dan,Mu Juan,Chen Xi,Chen Fasheng,Huang Xiaochuan,Tian Chen,Li Xiao,Wang Mengjun,Jiang Zhenju,Jiang Minghang
Electrocatalytic nitrate reduction (NITRR) serves as
a green and
promising strategy that combines eco-friendly ammonia (NH 3 ) synthesis and nitrate wastewater remediation. Nevertheless, various
nitrogenous side products together with the competitive hydrogen evolution
reaction (HER) render the reaction pathways intricate, bringing about
excess power loss and inferior product selectivity. Herein, mold-like
CuO@Co 3 O 4 nanocrystals with an abundance of
metal oxide heterojunction on carbon nanotubes (CNTs) were successfully
synthesized through a straightforward one-pot solvothermal approach.
Furthermore, the component proportion of CuO/Co 3 O 4 in the catalyst can be accurately tuned via modulating the molar
ratio between copper and cobalt precursors introduced in the synthetic
procedure. Compared to the alone CuO interface, the formation of the
CuO@Co 3 O 4 heterojunction interface effectively
modulates the catalyst’s capacity to activate water molecules
and generate reactive hydrogen species. This, in turn, substantially
facilitates the further selective hydrogenation of reactive species
adsorbed on the CuO interface to form NH 3 .The synthesized
CuO@Co 3 O 4 /CNTs catalyst demonstrates an impressive
Faradaic efficiency for NH 3 production ( FE NH 3 ) of 96.19 ± 0.71% at −0.8 V
vs RHE, even under extremely low nitrate concentrations, significantly
outperforming the CuO/CNTs counterpart. In addition, the assembled
NITRR||ZnOR cell with CuO@Co 3 O 4 /CNTs as cathode
and zinc foil as anode achieves a peak power density of 5.29 mW cm –2 when the discharge current density reaches 14 mA
cm –2 . The present research puts forward an innovative
design route for high-efficiency metal oxide heterojunction electrocatalysts
applied in nitrate electroreduction for ammonia synthesis.
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SEPARATION AND PURIFICATION TECHNOLOGY
·
2026
·
IF 9.1
Hao Fang,Wei Wang,Chenyi Wang,Xinyun Li,Menglan Xu,Ziyi Guo,Shengran Yu,Yanqing Cong,Shi-Wen Lv
Herein, for the first time, MOF-on-MOF-derived CuO/Co 3 O 4 composites with core-shell structure is prepared. The internal electric field formed at the heterojunction interface can accelerate charge transfer and offer more active sites, so enhancing the performance of CuO/Co 3 O 4 composites in formaldehyde degradation via peroxymonosulfate (PMS) activation. It is surprised to find that the adjustment of core and shell position in CuO/Co 3 O 4 composites has an important impact on the mechanism of PMS activation. Under the mediation of internal electric field, free electron will gather around Co 3 O 4 component of CuO/Co 3 O 4 composites. When Co 3 O 4 is served as the shell of CuO/Co 3 O 4 composite (marked as CuO/Co 3 O 4 –1), CuO/Co 3 O 4 composite will become electron donor and provide electron to activate PMS for producing SO 4 •– and OH • , which can oxidize formaldehyde into CO 2 and H 2 O. Interestingly, CuO/Co 3 O 4 composite will become electron acceptor when CuO is employed as the shell (denoted as CuO/Co 3 O 4 –2), so PMS can be easily oxidized into SO 5 •– and then decomposed into 1 O 2 . Due to the feature of 1 O 2 being moderate oxidation ability, formaldehyde can be selectively converted by 1 O 2 into formic acid with high economic value. Additionally, theoretical calculation based on density functional theory further proves these results. This work clarifies the effects of core and shell exchanges in CuO/Co 3 O 4 composite on catalytic activity, sharing some new insights for selective degradation of formaldehyde.
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