Materials
·
2026
·Vol. 19
·期 15
·3188
·
IF 3.7
Tianqi Cao,Hongyu Cui,Junyi Liu,Chuanhui Zhang
HighlightsCitric acid-assisted sol–gel method is adopted to synthesize a series of lanthanide-doped Co3O4catalysts.Sm-Co3O4delivers the smallest potential gap and dominates the high-efficiency 4-electron ORR pathway.Sm doping triggers lattice distortion and abundant oxygen vacancies, elevating the Co2+/Co3+ratio to 0.59.Lanthanide ion doping can simultaneously tune electronic structure and lattice defects of spinel Co3O4to enhance oxygen electrocatalytic activity.A structure–activity relationship linking lattice defects, Co valence states and catalytic performance is established.The sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) at air cathodes severely restrict the practical application of rechargeable zinc–air batteries (ZABs). Herein, equimolar lanthanide-doped spinel Co3O4bifunctional electrocatalysts were synthesized via a citric acid-assisted sol–gel method. Among Ce-, Pr-, La-, and Sm-doped catalysts, Sm-Co3O4exhibits the optimal electrocatalytic performance with a high ORR half-wave potential of 0.72 V and superior OER activity with an overpotential of 1.65 V at 10 mA cm−2, achieving a minimal potential gap ΔE of 0.93 V. Rotating ring-disk electrode (RRDE) measurements and Koutecky–Levich (K–L) analyses confirm the exclusive 4e−ORR pathway. Characterizations reveal that Sm doping modulates the electronic structure and lattice distortion of Co3O4, raises the Co2+/Co3+ratio (0.59) and creates abundant oxygen vacancies, thereby significantly lowering the overpotentials for both ORR and OER. This study provides new insights for designing high-performance spinel-based bifunctional electrocatalysts for ZABs.
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Surfaces and Interfaces
·
2026
·
IF 6
Shiyang Fu,Yuqing Shi,Guowei Yu,Xiao Liang,Nan Gao,Jing Zhang
Co 3 O 4 /Fe 2 O 3 p–n heterojunctions were prepared hydrothermally. • CF-5 shows a 5.6-fold response at a lower optimal temperature. • DFT reveals charge redistribution enhancing n-butanol adsorption. To selectively detect volatile organic compounds at low operating temperatures are highly desirable for industrial safety and environmental monitoring. Herein, we report the high-performance n-butanol gas sensors via interfacial engineering of Co 3 O 4 /Fe 2 O 3 p–n heterojunction composites. Hierarchical architectures composed of Fe 2 O 3 nanoparticles uniformly anchored on Co 3 O 4 nanorods were synthesized through a facile hydrothermal calcination strategy. Among the prepared samples, the optimized composite delivers a markedly enhanced sensing response of 23.08 toward 100 ppm n-butanol, representing a 5.6-fold improvement compared with pristine Co 3 O 4 , and simultaneously reducing the optimal operating temperature to 110°C. The mechanism analyses reveal pronounced interfacial charge transfer from Fe 2 O 3 to Co 3 O 4 , which induces band bending and built-in potential barriers that sensitively regulate carrier transport. The formation of heterointerfaces also significantly enriches chemisorbed oxygen species, thereby accelerating surface oxidation reactions with n-butanol molecules. As a result, the sensor exhibits outstanding selectivity against common interfering gases, fast response/recovery dynamics (42/36 s). Density functional theory calculations further elucidate that the heterojunction facilitates stronger adsorption of n-butanol and its oxidation intermediates, enhanced charge transfer, and favorable electronic-state redistribution near the Fermi level. This work highlights interfacial electronic engineering as an effective strategy for developing energy-efficient and highly reliable metal-oxide gas sensors. Download: Download high-res image (237KB) Download: Download full-size image
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JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2026
·
IF 9.6
Yuying Wang,Xiutao Yang,Guopeng Zhu,Haibin Niu,Shaoqing Zhang,Quanying Wang,Hongwen Yu
The accurate non-enzymatic electrochemical detection of glucose is constrained by sluggish charge transfer kinetics and non-optimized adsorption of reaction intermediates on single-phase transition metal oxide. Herein, we rationally design heterojunction Co 3 O 4 /NiMoO 4 hierarchical arrays, where a spontaneous built-in electric field (BEF) is formed at the p-n hereo-interface due to the precise work function difference in NiMoO 4 and Co 3 O 4 . This BEF directionally drives electrons from NiMoO 4 to Co 3 O 4 at 0.16 |e|, as confirmed by DFT charge density and Bader charge analysis, thereby accelerating glucose electrocatalytic oxidation kinetics. Moreover, the hierarchical structure of Co 3 O 4 nanoneedles grown on NiMoO 4 nanorods enhances the electrochemical active area and introduces dual catalytic sites of Co and Ni atoms, whose d-band centers are modulated to weaken excessive adsorption at Co sites while maintaining Ni activity. As a results, the assembled sensor achieves an ultrahigh sensitivity of 28,470 μA mM −1 cm −2 , a low detection limit of 0.396 μM and excellent recovery rates (94.6%–105.6%) in complex real samples. This work demonstrates that resolving the charge transfer and adsorption trade-off via BEF-engineered heterostructure offers a generalizable route for high-performance sensing. Download: Download high-res image (156KB) Download: Download full-size image
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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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JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS
·
2026
·
IF 5.9
Jian Zhang,Kaixin Xia,Ningruo Wang,Xuewen Xie,Siyi Liao,Biao Zhong,Xuejian Zhang
Co 3 O 4 @AC composite was successfully synthesized for efficient PMS activation. • The AC support can effectively inhibit the self-aggregation of Co 3 O 4 nanoparticles. • 97.47% of bisphenol AF can be removed within 60 min in the Co 3 O 4 @AC/PMS system. • A dual radical/non-radical oxidation mechanism was confirmed, with 1 O 2 and SO 4 · - as the dominant active species. • The composite exhibited excellent cyclic stability with low cobalt leaching. Bisphenol AF (BPAF) is a typical refractory fluorinated organic pollutant with strong biological toxicity and poor biodegradation, posing potential hazards to aquatic ecosystems and human health. Peroxymonosulfate (PMS)-based advanced oxidation processes (AOPs) have been widely recognized as efficient treatment technologies for organic wastewater, while the agglomeration of pure cobalt-based catalysts limits their practical activation and degradation performance. In this work, a Co 3 O 4 @AC catalyst was successfully constructed by a simple impregnation-calcination method using porous activated coke (AC) to load Co 3 O 4 nanoparticles. Structural characterization proved the successful loading of Co 3 O 4 on the AC carrier. The optimized Co 3 O 4 @AC composite achieved a satisfactory BPAF removal efficiency of 97.47% within 60 min. Electron paramagnetic resonance (EPR) tests and radical quenching experiments indicated that BPAF removal was primarily attributed to both radical and non-radical pathways, with SO 4 · - and 1 O 2 as the crucial active species. DFT calculations indicated that benzene rings and phenol hydroxyl groups were the primary reaction sites of BPAF. Two possible degradation pathways of BPAF were proposed, combined with the identified intermediate products. Furthermore, the composite exhibited excellent cyclic reusability and a low risk of cobalt ion leaching. This work provides a feasible strategy for treating fluorinated refractory wastewater and deepens the mechanistic understanding of carbon-supported metal oxide catalysts during PMS activation.
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JOURNAL OF RARE EARTHS
·
2026
·
IF 9.6
Jing Xuan,Olga Kelebogile Mmelesi,Yali Yao,Zhen Wang,Shuai Lyu,Xiao Xu,Zhiyan He,Jie Yang,Ping Xiao,Junjiang Zhu
Atomic-level engineering of the surface and electronic structure of Co 3 O 4 catalysts holds significant importance for both fundamental catalytic mechanisms and practical applications. In this study, well-defined La single atom-doped Co 3 O 4 catalysts were designed via an ion exchange process. Theoretical and experimental analyses demonstrate that single La atoms selectively substitute Co 3+ ions at octahedral sites in Co 3 O 4 . The larger ionic radius of La induces compressive strain on adjacent atoms, resulting in localized lattice distortion. To release the local tension, an asymmetric La–V o –Co site spontaneously forms. The coordination number of La decreases from 6 to 4.7 due to vacancy formation, leading to a reduced valence state and enhanced electron-donating propensity. Theoretical calculations reveal that single-atom La doping leads to an upshift of the Co 3 O 4 d-band center, thereby enhancing its interaction with oxygen. Besides, electrons from the 5d orbitals of La transfer to the π * antibonding orbitals of molecular oxygen during catalytic oxidation, thereby weakening the O–O bond strength and promoting oxygen dissociation. The single-atom La modified Co 3 O 4 catalyst exhibits remarkable catalytic activity in the oxidation of benzyl alcohol (BzOH), resulting in a 4.5-fold increase in conversion rate compared to unmodified Co 3 O 4 . The findings of our research provide a robust foundation for the characterization and comprehension of single-atom rare earth catalysts in heterogeneous oxidation reaction.
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Nano Materials Science
·
2026
·
IF 20.5
Meng Mei,Kaixin Cheng,Yi Zheng,Bo Yao,Juan Wu,Zilian Zhang,Xinxin Xing,Yude Wang
Early warning of thermal runaway in lithium-ion batteries (LIBs) is a critical challenge for ensuring operational safety. Conventional monitoring approaches based on temperature and voltage are often limited by delayed response and susceptibility to environmental interference. In contrast, gas monitoring presents a promising alternative. Key electrolyte components such as dimethyl carbonate (DMC) are released during the early stages of thermal runaway, preceding gases like hydrogen and carbon monoxide, offering a unique opportunity for early warning. However, current DMC gas sensors are often hampered by the high operating temperatures and the sluggish response/recovery dynamics. In this work, we developed a gas sensor based on a Co 3 O 4 -ZnO p-n heterojunction. Under the operating temperature of 160 °C, the sensor exhibits a high response value of ∼110 to 500 ppm DMC, along with rapid response and recovery times (2 s and 15 s, respectively), as well as excellent selectivity against interfering gases such as H 2 , CO, and so on. The sensor also demonstrates stable performance over 32 d. Material characterization and theoretical calculations reveal that the p-n heterojunction effectively enhances carrier density and oxygen vacancy concentration, thereby facilitating DMC adsorption and electron transfer. Through simulated battery electrolyte leakage experiments, the sensor's capability for real-time and rapid detection of DMC is validated, highlighting its potential as an effective solution for early warning of thermal runaway in LIBs.
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ELECTROANALYSIS
·
2026
·Vol. 38
·期 4
·e70143
·
IF 2.6
Hongying Wang,Ran Zhang,Minzi Li,Shaohong Zhang,Ying Wu,Zhijuan Wang
Nanozymes have attracted considerable attention as a promising class of artificial enzymes with significant development potential in recent years. Herein, a nitrogen-doped hollow porous carbon nanocomposite embedded with Co 3 O 4 nanoparticles (Co 3 O 4 -HPNC) was successfully synthesized through the controlled carbonization and subsequent slow oxidation of bimetallic Co/Zn zeolitic imidazolate frameworks (ZIFs). The Co 3 O 4 -HPNC features a hollow architecture conposed of numerous small nanoparticles, forming a porous flocculent morphology that enhances mass transport efficiency. It exhibited remarkable peroxidase-like activity, catalyzing the oxidation of colorless 3,3 ′ , 5,5 ′ -tetramethylbenzidine (TMB) to blue oxidized TMB (oxTMB) in the presence of H 2 O 2 . This reaction was driven by the generation of hydroxyl radicals (·OH), as confirmed by fluorescence and electron paramagnetic resonance (EPR) results. Notably, the oxidization process was significantly inhibited by the addition of L-cysteine (L-Cys), leading to a visible fading of the blue color and a corresponding decrease in UV–vis absorbance. Moreover, Co 3 O 4 -HPNC demonstrated good selectivity and strong anti-interference capability toward L-Cys detection. Based on these findings, a simple and effective colorimetric method was developed for quantifying L-Cys with a linear range of 1–50 μM and a detection limit of 0.13 μM (S/N = 3). This Co 3 O 4 -HPNC-based colorimetric platform holds significant potential for applications in biosensors and clinic diagnostics.
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Journal of Environmental Chemical Engineering
·
2026
·Vol. 14
·期 2
·122053
·
IF 7.5
Ting Shen,Ao Cheng,Dong Chen,Dan Wang,Yafei Zhao,Bing Zhang
The contamination of aqueous environments by antibiotics necessitates efficient remediation strategies, among which cobalt-based advanced oxidation processes (AOPs) have garnered significant attention for their high degradation efficiency. Herein, we utilized N self-doped biochar (SDBC) with a high specific surface area derived from Ginkgo biloba leaves as a support for the in-situ growth of Co 3 O 4 nanoparticles via one-pot pyrolysis. The optimized Co 3 O 4 /N-SDBC-800 catalyst exhibited outstanding activity for tetracycline (TC) degradation through peroxymonosulfate (PMS) activation, achieving a remarkable 98.47% removal efficiency within 5 min. The corresponding rate constant was 0.241 min −1 , surpassing most previously reported values. Moreover, the Co 3 O 4 /N-SDBC-800/PMS system displayed robust performance over a wide pH range (maintaining >90% TC removal efficiency from pH 3–11) and exceptional operational versatility in diverse aqueous matrices. Mechanistically, the degradation pathway was revealed to be predominantly governed by non-radical processes, as evidenced by radical quenching experiments and electron paramagnetic resonance (EPR) analysis. Singlet oxygen ( 1 O 2 ) was identified as the principal reactive species responsible for the catalytic oxidation of the organic pollutants. The synergistic coupling of heteroatom N-doping and graphitization was found to create active sites and reconfigure the electronic structure, thereby facilitating charge transfer and ultimately accelerating the decomposition of TC.
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Biochar
·
2026
·Vol. 8
·期 1
·113
·
IF 15.1
Zhang Jian,Xie Jiafang,Zhu Shuhui,Yang Jiacheng E.,Weng Bo,Zheng Yuming
Biochar optimized with oxygen-containing functional groups is believed to be beneficial for peroxymonosulfate (PMS) activation, and biochar-loaded Co 3 O 4 -based catalysts are expected to be one of the most promising PMS activators for the efficient removal of organic pollutants. Nevertheless, the real active sites on Co 3 O 4 catalysts are still in debate due to insufficient experimental evidence. Herein, Co 3 O 4 growing on the oxygen-containing functional groups optimized rice husk biochar (RHBA) was synthesized (RHBA@Co 3 O 4 ), and RHBA800@25Co 3 O 4 + PMS system achieved complete degradation (100%) of refractory levofloxacin (LFX) within 4 min. The superior catalytic performance was suggested to be attributed not only to the uniform dispersion of Co 3 O 4 , but also to the transformation of lattice oxygen in Co 3 O 4 , which was found to play an important role in the catalytic process by inducing the formation of Co 3 O 4−α –OH. Meanwhile, density functional theory (DFT) calculations indicated that the adsorption energy ( E ads ) of PMS on Co 3 O 4−α –OH was far lower than that on Co 3 O 4 . Moreover, both radical and non-radical pathways were indicated to be involved during the degradation process. Additionally, the practical application of RHBA@Co 3 O 4 was investigated using various antibiotics, actual water environments, and fixed-bed reactors. The results showed that it possessed good practical degradation performance and significantly reduced the toxicity of intermediate products. This work provides a fresh insight into the catalytic mechanism of RHBA800@25Co 3 O 4 for PMS activation and wastewater treatment, offering a new perspective on the catalytic mechanism of Co 3 O 4 -based materials. Highlights
RHBA800@25Co 3 O 4 exhibited ultrafast antibiotics degradation via peroxymonosulfate activation.
Inspired formation of Co 3 O 4−α –OH by lattice oxygen induction was explored.
Ecological safety of levofloxacin degradation products was verified through antibacterial experiments.
Graphical The alternative text for this image may have been generated using AI.
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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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ACS Omega
·
2026
·Vol. 11
·期 32
·47638-47653
·
IF 5.2
Liu Yanchi,Sun Mohan,Qian Chengchao,Fu Yabo,Qiao Junwei,Wang Diangang,Shi Jiazi,Zhang Gaimei,Zhang Xinlin,Liu Hui
To overcome the poor
visible light response and high
recombination
rate of photogenerated carriers in bare TiO 2 , a Pt/Co 3 O 4 /TiO 2 photocatalyst was fabricated
via a template-assisted spontaneous galvanic replacement route. The
as-prepared material contains anatase–rutile mixed-phase TiO 2 , Co 3 O 4 , and metallic Pt and retains
a dodecahedral morphology with a high specific surface area of 122.64
m 2 /g. Under visible light irradiation for 120 min, its
degradation rates for tetracycline and methylene blue reached 85%
and 93%, respectively, which are significantly better than those of
pure TiO 2 and Pt/Co 3 O 4 . The composite
also exhibited excellent stability and recyclability. Its superior
performance is ascribed to the synergistic effects of the mixed-phase
TiO 2 , the p–n heterojunction between TiO 2 and Co 3 O 4 , the Schottky barrier at the Pt/TiO 2 interface, the localized surface plasmon resonance of Pt,
and the high adsorption capacity of the porous material. This work
offers a new strategy for treating dye- and antibiotic-containing
wastewater.
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