High-valent Cobalt Research Articles

Engineering the Co/CoO heterostructure to trigger the in-situ generation of abundant high-valent cobalt species for enhanced electroreduction of nitrate to ammonia

The CoO-based materials are promising candidates for electrochemical nitrate reduction reaction to ammonia (eNO3RR). Herein, Zn/Co bimetallic MOFs are adopted to construct Co/CoO Schottky heterostructures, where the Co-CoO interfaces are engineered by controlling the Zn/Co ratio. The interface-optimized Co/CoO displays an NH3 yield of 713 µmol/h cm−2 and a maximum Faradaic efficiency of 99.16 % due to the synergistic effect between CoO and Co and abundant oxygen vacancies. The more the Co-CoO interfaces, the more the in-situ generated high-valent cobalt species (CoOOH), and the higher the catalytic performance. Therefore, the high-valent cobalt species are considered the true active sites. When used as a cathode in a rechargeable Zn-NO3− battery, the Co/CoO heterostructure achieves a power density of 4.7 mW cm−2 and an NH3 yield of 131.7 µmol/h cm−2 with robust working stability.

Rapid Peracetic acid activation by CoO under neutral condition: The contribution of multiple reactive species

This paper proposes a novel process of cobalt monoxide (CoO)-activated peracetic acid (PAA) for treating emerging micropollutant in water. PAA was activated under neutral conditions by combining a dominant heterogeneous phase on the catalyst surface and a homogeneous phase by dissolved Co2+. The system produced several reactive oxygen species, including hydroxyl radicals (HO∙HO•), singlet oxygen (1O2), organic radicals (RO•(CH3C(O)O•, CH3C(O)OO•) and high-valent cobalt (Co(IV)). Organic radicals and high-valent cobalt primarily drove the emerging micropollutants degradation, interacting via electron transfer. Further density functional theory calculations supported that the spontaneous adsorption of PAA onto the catalyst could break peroxy bonds that generate radicals. Furthermore, the CoO surface structure underwent minimal changes during the reaction, making it highly reusable. Thus, the novel CoO/PAA system could be an effective advanced oxidation process for water treatment.

Isolation and Crystallographic Characterization of an Octavalent Co2O2 Diamond Core.

High-valent cobalt oxides play a pivotal role in alternative energy technology as catalysts for water splitting and as cathodes in lithium-ion batteries. Despite this importance, the properties governing the stability of high-valent cobalt oxides and specifically possible oxygen evolution pathways are not clear. One root of this limited understanding is the scarcity of high-valent Co(IV)-containing model complexes; there are no reports of stable, well-defined complexes with multiple Co(IV) centers. Here, an oxidatively robust fluorinated ligand scaffold enables the isolation and crystallographic characterization of a Co(IV)2-bis-μ-oxo complex. This complex is remarkably stable, in stark contrast with previously reported Co(IV)2 species that are highly reactive, which demonstrates that oxy-Co(IV)2 species are not necessarily unstable with respect to oxygen evolution. This example underscores a new design strategy for highly oxidizing transition-metal fragments and provides detailed data on a previously inaccessible chemical unit of relevance to O-O bond formation and oxygen evolution.

Cooperation of Strong Electric Field and H2O Dissociation on Co3O4-Decorated SiC Rods for Photodriven CO2 Methanation with 100% Selectivity.

Solar-driven methanation of carbon dioxide (CO2) with water (H2O) has emerged as an important strategy for achieving both carbon neutrality and fuel production. The selective methanation of CO2 was often hindered by the sluggish kinetics and the multiple competition of other C1 byproducts. To overcome this bottleneck, we utilized a biomass synthesis method to synthesize SiC rods and then constructed a direct Z-scheme heterojunction Co3O4/SiC catalyst. The substantial difference in work functions between SiC and Co3O4 served as a significant source of the charge driving force, facilitating the conversion of CO2 to CH4. The high-valent cobalt Co(IV) in Co3O4 acts as an active species to promote efficient dissociation of water. This favorable condition greatly enhanced the likelihood of a high concentration of electrons and protons around a single site on the catalyst surface for CO2 methanation. DFT calculation showed that the energy barrier of CO2 hydrogenation was significantly reduced at the Co3O4/SiC heterojunction interface, which changed the reaction pathway and completely converted the product from CO to CH4. The optimum CH4 evolution rate of Co3O4/SiC samples was 21.3 μmol g-1 h-1 with 100% selectivity. This study has an important guiding significance for the selective regulation of CO2 to CH4 products in photocatalysis applications.

Bimetallic cobalt-cerium oxides activated fenton-like process for organic contaminant removal: Role of high-valent cobalt species modulated by oxygen vacancies

Cobalt-cerium bimetallic oxides (CoCeOx) with rich oxygen vacancies (OVs) were prepared by solvothermal method for peroxymonosulfate (PMS) activation efficiently, and the effect of OVs on reactive species formation was discussed. Carbamazepine (CBZ), a widely used anti-epileptic drug, also a typical pharmaceutical and personal care products (PPCPs) in the water environment, could be removed by 98 % in 40 min with low addition of CoCeOx and PMS in the CoCeOx/PMS system. Through a series of quenching experiments and electron paramagnetic resonance, it was confirmed that the main reactive species for decontamination were high-valent cobalt oxygen species (Co(IV)). Through the OVs detection and the contribution calculation of radicals and non-radicals on CBZ removal, it was found that OVs promoted the transformation from radicals to non-radicals (mainly Co(IV)) in the systems. In addition, cerium doping played an important role in promoting Co (II) / Co (III) cycle and OVs regeneration. Density functional theory (DFT) calculation revealed the formation process of Co(IV), and further proved that OVs could promote the formation of Co(IV). Evaluated by quantitative structure–activity relationship (QSAR) analysis, the ecotoxicity of CBZ and its main intermediates was significantly decreased. Overall, this study deepens the understanding of OVs promoting the formation of high-valent metal oxygen species (HVMO), as well as provides feasibility for the removal of refractory organics in wastewater.

Selective oxidation decontamination in cobalt molybdate activated Fenton-like oxidation via synergic effect of cobalt and molybdenum

In this study, cobalt molybdate (CoMoO4) activated peracetic acid (PAA) was developed for water purification. CoMoO4/PAA system could remove 95% SMX with pseudo-first-order reaction rate constant of 0.15410 min−1, which was much higher than CoFe2O4/PAA, FeMoO4/PAA, and CoMoO4/persulfate systems. CoMoO4/PAA system follows a non-radical species pathway dominated by the high-valent cobalt (Co(IV)), and CH3C(O)OO• shows a minor contribution to decontamination. Density functional theory (DFT) calculation indicates that the generation of Co(IV) is thermodynamically more favorable than CH3C(O)OO• generation. The abundant Co(IV) generation was attributed to the special structure of CoMoO4 and effect of molybdenum on redox cycle of Co(II)/Co(III). DFT calculation showed that the atoms of SMX with higher ƒ0 and ƒ- values are the main attack sites, which are in accordance with the results of degradation byproducts. CoMoO4/PAA system can effectively reduce biological toxicity after the reaction. Benefiting from the selective of Co(IV) and CH3C(O)OO•, the established CoMoO4/PAA system exhibits excellent anti-interference capacity and satisfactory decontamination performance under actual water conditions. Furthermore, the system was capable of good potential practical application for efficient removal of various organics and favorable reuse. Overall, this study provides a new strategy by CoMoO4 activated PAA for decontamination with high efficiency, high selectivity and favorable anti-interference.

Radiation-induced preparation of nanoscale CoO@graphene oxide for activating peroxymonosulfate to degrade emerging organic pollutants

In this study, ionizing radiation was used to induce the in-situ formation of highly dispersed nanosized cobalt oxide on the surface of graphene oxide (R-Co-GO), which was highly effective for activating PMS to degrade sulfamethoxazole (SMX). R-Co-GO had the highest catalytic activity when 150 μL cobalt chloride hexahydrate solution was used in the precursor, and the pseudo first-order kinetic constant of SMX degradation was 0.07 min−1 with high mineralization efficiency (63.1 %) and high PMS utilization efficiency. The sulfate radicals and high-valent cobalt oxo were mainly responsible for SMX degradation. Mechanism analysis showed that cobalt active site dominated in PMS activation, which was responsible for the formation of sulfate radicals and high-valent cobalt oxo; while the carbon framework contributed to the formation of singlet oxygen. The R-Co-GO-150 had good catalytic activity and stability in five cycling experiments, in which SMX was completely degraded and the concentration of dissolved Co was below 0.1 mg/L. In addition, the R-Co-GO-150/PMS system could also degrade phenol, bisphenol A, atrazine and nitrobenzene effectively, confirming its wide applicability. This study provided a facile method to uniformly disperse the metal oxides on the surface of carbon materials, and an effective system for the removal of emerging organic pollutants from the actual wastewater.

Reinvestigation on High-Valent Cobalt for the Degradation of Micropollutants in the Co(II)/Peroxymonosulfate System: Roles of Co(III)

Reinvestigation on High-Valent Cobalt for the Degradation of Micropollutants in the Co(II)/Peroxymonosulfate System: Roles of Co(III)

Vitamin C-regulated CoAl- layered double hydroxide with oxygen vacancies to efficiently activate peroxydisulfate for sulfamethoxazole removal triggered via reactive oxygen and high-valent cobalt species

In this study, a vitamin C-regulated CoAl-layered double hydroxide with abundant oxygen vacancies was synthesized via a simple hydrothermal process. The resulting CoAl-layered double hydroxide was employed to activate peroxydisulfate for removal of sulfamethoxazole. The effect of the experimental parameters such as pH, catalyst dose and peroxydisulfate concentration on sulfamethoxazole removal was investigated. The current system exhibited excellent catalytic performance for sulfamethoxazole removal in a broad pH range (i.e., pH 3.0–11.0). Under the optimized condition, 94.2% of sulfamethoxazole was degraded within 15 min, accompanied by a 67.6% reduction in chemical oxygen demand. The effective sulfamethoxazole degradation could be attributed to four pathways. Firstly, the ≡ Co2+ in catalyst reacted with peroxydisulfate to generate reactive species, including SO4•−, •OH, O2•− and 1O2, which could degrade sulfamethoxazole. Secondly, the oxygen vacancies could modulate intrinsic electrons, resulted in the surface activation of catalyst and accelerated charge transfer, which was favorable for the degradation of sulfamethoxazole. Thirdly, the presence of vitamin C not only promoted the formation of oxygen vacancies but also expanded the interlayer spacing of layered double hydroxide. A large interlayer spacing facilitated the diffusion of peroxydisulfate and pollutants in the interlayer and improved the utilization efficiency of the active site. Lastly, the high-valent cobalt species exhibited excellent oxidation ability and enhanced the catalyst performance through continuously being employed as an electron acceptor. This study provided a valuable insight for the design and application of Co-based catalysts in peroxydisulfate-based advanced oxidation processes.

Cation defect engineering in LaCoO3 perovskite as the “Two birds one stone” strategy to enhanced Fenton-like reaction: Regulating Co spin state and optimizing electron transfer ability

The reactive oxygen species (ROS) triggered by peroxymonosulfate (PMS), primarily composed of radicals and nonradicals, can deeply and selectively remove pollutants in complex wastewater. However, the low efficiency of electron transfer and insufficient surface catalytic sites remain the main obstacles to the development of efficient and selective PMS activators. Herein, we constructed ABO3 perovskite catalysts (LaCoO3) with adjustable La vacancies (VLa) densities through urea introduction. Experiment, characterization, and theoretical calculation jointly revealed that VLa could not only induce electron delocalization in Co site to enhance the Co 3d − O 2p covalency for accelerating ROS (sulfate radicals (SO4−), singlet oxygen (1O2), and high valent cobalt (Co(IV) = O)) generation, but also trigger the transition of spin-polarization configuration to form Co3+ (t2g5eg1) with the intermediate spin state as new active sites for surface-bound PMS* complexes production. The nonradical-dominated and radical-assisted system containing multi-site achieved efficient PMS utilization (95.6 %), excellent decontamination activity (0.753 min−1), good mineralization ability (82.7 %), satisfactory acid-base resistance (working pH range 3–11), and environmental robustness for actual water treatment. This study reveals the role of cation vacancy engineering in achieving “Two birds one stone” for PMS activation at the atomic level, which will guide the rational design of Fenton-like catalysts.

Co(CO3)0.5(OH)•0.11H2O as superior peroxymonosulfate activator for ciprofloxacin degradation via co-acting mechanism of low & high-valent cobalt and oxygen vacancy

In this study, oxygen vacancies-rich (OVs-rich) Co(CO3)0.5(OH)•0.11H2O catalyst was prepared by a hydrothermal process, which was used to activate peroxymonosulfate (PMS) and degrade ciprofloxacin (CIP). Although its specific surface area was only 46.2 m2 g−1, the Co(CO3)0.5(OH)•0.11H2O catalyst exhibited high performance. Under its natural pH, 91.0% of CIP (50 ppm) was degraded and chemical oxygen demand removal reached 70% in 10 min. The rapid degradation reaction followed Behnajady-Modirshahla-Ghnbery kinetic model. The research on catalytic mechanism indicated that three coexisting catalytic pathways resulted in the efficient degradation of CIP. (1) The low-valent Co2+ in Co(CO3)0.5(OH)•0.11H2O activate PMS to generate four kinds reactive oxygen species such as SO4•−, •OH, O2•− and 1O2. (2) The dissolved oxygen was adsorbed on Co(CO3)0.5(OH)•0.11H2O surface and the abundant localized electrons of OVs made them easily endow electrons to O2, reducing O2 to O2•− and then to 1O2. (3) The reaction between the Co2+ and PMS resulted in the high-valent Co4+(O) species, which possessed outstanding oxidation ability for CIP degradation.

Enantioselective C-H bond functionalization under Co(III)-catalysis.

While progress in enantioselective C-H functionalization has been accomplished by employing 4d and 5d transition metal-based catalysts, the rapid depletion of these metals in the earth's crust poses a serious threat to making these protocols sustainable. On the other hand, because of their unique reactivity, low toxicity, and high earth abundance, newer strategies utilizing affordable 3d transition metals have come to the forefront. Among the first-row transition metals, high-valent cobalt has recently attracted a lot of attention for catalytic C-H functionalization with mono and bidentate directing groups. This approach was extended for asymmetric catalysis due to a fairly thorough knowledge of its catalytic cycles. Four major themes have been investigated as a result of this insight: (1) rational design of a chiral Cp#Co(III)-catalyst, (2) chiral carboxylic acid with achiral Cp*Co(III)-catalysts using monodentate directing groups, (3) cobalt/salox-based systems, and (4) cobalt/chiral phosphoric acid-based hybrid systems with bidentate directing groups. Herein, we highlight the recent developments in high-valent cobalt-catalyzed enantioselective C-H functionalization up to October 2023, with the strong belief that the current state-of-the-art can attract considerable interest in the synthetic community, encouraging discoveries in the evolving landscape of asymmetric catalysis.

Copper dopants facilitated generation of high-valent cobalt sites for improved oxygen evolution

We report a strategy for adjusting surface reconstruction of Co4N, in which inert Co3O4 on the reconstruction surface is activated via Cu introduction (Cu-Co4N), facilitating the deprotonation process to generate CoO2.

Peroxyacetic acid activation by cobalt-doped peanut shell biochar for efficient CBZ degradation: Role of organic radicals, singlet oxygen, and high-valent cobalt species

Peroxyacetic acid (PAA) oxidant has a broad application prospect to be combined with biochar in the treatment of organic pollutants due to its excellent characteristics of eco-friendly and easy activation. In this study, peanut shell biochar-loaded Co nanoparticles (Co-BC-850) catalysts were prepared through pyrolysis to activate PAA for carbamazepine (CBZ) degradation. The pyrolysis temperature significantly affected the CBZ degradation efficiency of the catalysts. The experimental results revealed that the Co-BC-850 catalyst exhibited the highest CBZ degradation efficiency. Within 20 min, a CBZ degradation rate of 99.9% was achieved with Co-BC-850 concentration of 50 mg/L and PAA concentration of 1 mM. The Co-BC-850/PAA system achieved high degradation performance for CBZ at a pH ranging from 5.0 to 9.0, even in the presence of inorganic anions. The analysis of the Co-BC-850/PAA system revealed a complex interplay of reactive species (RSs). Organic radicals (R-O•), singlet oxygen (1O2), and high-valent cobalt species (Co(IV)) collaboratively contributed to CBZ degradation. These findings revealed the intricate mechanism of CBZ degradation via Co-BC-850-activated PAA, thereby elucidating potential degradation pathways. This study demonstrates the promising application of biochar PAA-based AOPs and offers a sustainable and effective solution for the degradation of CBZ and other potential pharmaceutical compounds in water.

Spatial confinement-regulated peroxymonosulfate activation to boost the generation of high-valent cobalt and radical species for achieving rapid removal of organic pollutants

It is of great significance to establish simple and effective methods to tackle water pollution problems. Herein, Co-loaded hollow carbon sphere (namely Co-HCS-1) served as PMS activation mediator was synthesized. The construction of hollow structure can improve specific surface areas and offer more active sites, thereby reducing electron transfer resistance and increasing contact among PMS, pollutant and catalyst. Hence, the Co-HCS-1-mediated direct electron-transfer oxidation between PMS and pollutant was enhanced. After embedding Co-based catalyst in the shell of hollow carbon sphere, hollow carbon shell will provide spatial confinement for Co-based catalyst, which shortened mass transfer process. Thus, spatial confinement effect originating from carbon sphere can accelerate the charge transfer between PMS and active sites of Co-HCS-1, thereby promoting O-O bond cleavage of PMS. As a result, the generations of radicals and high-valent metal complexes (namely Co-HCS-1≡Co4+) were boosted. Under the combined effects of electron-transfer oxidation, reactive oxygen species and Co-HCS-1≡Co4+, more than 90 % of typical organic pollutants can be removed from simulated wastewater within 5 min by Co-HCS-1/PMS system, and a high removal efficiency of total organic carbon can also be realized. To sum up, current work provided a valuable reference for the preparation and application of catalyst with high activity in PMS activation.

High-valent cobalt active sites derived from electrochemical activation of metal-organic frameworks for efficient nitrate reduction to ammonia

Metal-organic frameworks (MOFs) exhibited great potential in the electrocatalytic reduction of nitrate to ammonia (eNO3RR), but the structural transformation and the identification of the active sites in the electrochemical process have rarely been reported. Herein, a series of MOFs have been fabricated for eNO3RR. The Co-based MOF (Co-TPA) is selected as a representative for exploration through in-situ and ex-situ techniques to reveal the structural evolution during eNO3RR. The structural transformation from the Co-TPA to electrochemically activated catalyst (Co-TPA-E) is verified, and it is found that the in-situ formed high-valent Co species (CoOOH) are the active sites for eNO3RR. Moreover, the formation of the high-valence CoOOH species can be further facilitated by introducing highly electronegative Cu ions into the Co-TPA-E, resulting in excellent catalytic activity with an NH3 yield rate of 1.12 mmol h−1 cm−2 at − 0.326 V vs. RHE and a maximum Faradaic efficiency of 99.62 %.

Study on the mechanism of sulfur poisoning in toluene catalyzed by Co3O4/γ-Al2O3 sulfur tolerant catalyst containing spinel structure

In this paper, in-situ thermal decomposition of ammonium sulfate method was used to cause sulfur poisoning of Co3O4/γ-Al2O3 catalyst rapidly and quantitatively. The pore structure, valence state of active species, surface morphology and acidity of the catalyst before and after sulfur poisoning were characterized, and its influence on catalytic combustion of toluene was studied. The results showed the crystal shape of the catalyst changed little after sulfur poisoning. As sulfur poisoning gradually deepened, the formation of sulfate blocked the pores, the high-valence cobalt decreased, strong acid sites increased, and its catalytic activity for toluene combustion gradually decreased. Formation of cobalt sulfate was a main reason for the decline in catalyst activity. Spinel phase CoAl2O4 formed outside γ-Al2O3 framework can adsorb a large amount of sulfur species to form sulfate, protecting Co3O4 and delaying the deactivation of catalysts.

Temperature-Driven Anisotropic Mg2+ Doping for a Pillared LiCoO2 Interlayer Surface in High-Voltage Applications.

High-voltage lithium cobalt oxide (LiCoO2) has the highest volumetric energy density among commercial cathode materials in lithium-ion batteries due to its high working voltage and compacted density. However, under high voltage (4.6 V), the capacity of LiCoO2 fades rapidly due to parasitic reactions of high-valent cobalt with the electrolyte and the loss of lattice oxygen at the interface. In this study, we report a temperature-driven anisotropic doping phenomenon of Mg2+ that results in surface-populated Mg2+ doping to the side of the (003) plane of LiCoO2. Mg2+ dopants enter the Li+ sites, lower the valence state of Co ions with less hybridization between the O 2p and Co 3d orbitals, promote the formation of surface Li+/Co2+ anti-sites, and suppress lattice oxygen loss on the surface. As a result, the modified LiCoO2 demonstrates excellent cycling performance under 4.6 V, reaching an energy density of 911.2 Wh/kg at 0.1C and retaining 92.7% (184.3 mAh g-1) of its capacity after 100 cycles at 1C. Our results highlight a promising avenue for enhancing the electrochemical performance of LiCoO2 by anisotropic surface doping with Mg2+.

Low-coordinated Co-N3 sites induce peroxymonosulfate activation for norfloxacin degradation via high-valent cobalt-oxo species and electron transfer

The identification of reactive species in peroxymonosulfate (PMS) activation triggered by carbon-based single atom catalysts is the key to reveal the pollutant degradation mechanism. Herein, carbon-based single atom catalyst with low-coordinated Co-N3 sites (CoSA-N3-C) was synthesized to active PMS for norfloxacin (NOR) degradation. The CoSA-N3-C/PMS system exhibited consistent high performance for oxidizing NOR over a wide pH range (3.0–11.0). The system also achieved complete NOR degradation in different water matrixes, high cycle stability and excellent degradation performance for other pollutants. Theoretical calculations confirmed that the catalytic activity was derived from the favorable electron density of low-coordinated Co-N3 configuration, which was more conductive to PMS activation than other configurations. Electron paramagnetic resonance spectra, in-situ Raman analysis, solvent exchange (H2O to D2O), salt bridge and quenching experiments concluded that high-valent cobalt(IV)-oxo species (56.75%) and electron transfer (41.22%) contributed dominantly to NOR degradation. Moreover, 1O2 was generated in the activation process while not involved in pollutant degradation. This research demonstrates the specific contributions of nonradicals in PMS activation over Co-N3 sites for pollutant degradation. It also offers updated perceptions for rational design of carbon-based single atom catalysts with appropriate coordination structure.

Synergistic effect of high-valent cobalt oxo species and piezoelectricity on enhanced peroxymonosulfate activation for atrazine removal

Co-based catalysts, especially the role of high-valent cobalt oxo species (Co(IV)) have made considerable progress in the field of the advanced oxidation process based on peroxymonosulfate. Nevertheless, the unsatisfactory efficiency drives to find of a suitable method to enhance the electron transfer for the improved performance of Co-based catalyst/PMS systems. Here, Enteromorpha-derived biochar modified with cobalt and barium titanate (CoBCBa) was prepared by pyrolysis. It can completely remove atrazine (10 mg/L) within 30 min under ultrasonic, and exhibited strong environmental tolerance. The superior performance of CoBCBa is attributed to the synergistic effect of Co(IV) and the piezoelectricity of BaTiO3. The apparent reaction rate under the ultrasonic condition was 1.61 times higher than that non-ultrasonic condition. The density functional theory calculation indicates that the reduction of the energy barrier in the CoBCBa/PMS system is beneficial to the production of Co(IV). This work provides novel guidance for constructing piezoelectricity assisted high-valent cobalt oxo species to treat organic pollutants in environmental remediation.