Co-N4 Sites Research Articles

Z-scheme heterojunction TNCoPc/BiOBr nanomicrospheres for efficient photodegradation of tetracycline and rhodamine B: Degradation performance, intrinsic mechanism and degradation pathway studies

The natural ecosystem has been significantly jeopardized due to the misuse of organic dyes and antibiotics. To treat organic wastewater safely and efficiently, this study synthesized a binary composite photocatalyst TNCoPc/BiOBr, using a solvothermal method that involved loading cobalt tetranitro phthalocyanine onto BiOBr. The results of the catalytic performance tests indicated that the composites exhibited the capacity to degrade rhodamine B and tetracycline hydrochloride by 97.75 % and 78.37 %, respectively. Moreover, the composite exhibited good cyclic stability. Subsequent analytical characterization confirmed the formation of a Z-scheme heterojunction, resulting in a synergistic effect. This Z-scheme heterojunction facilitated the capacity of photocatalyst to achieve enhanced light absorption, augmented photogenerated carrier separation efficiency, and augmented redox capacity. Additionally, theoretical calculations were employed to further elucidate the catalytic mechanism and synergistic effects. The results demonstrate that the Co-N4 sites are the active center of the TNCoPc and verify the contribution of nitro substitution to the photogenerated electron transfer mechanism on TNCoPc. Furthermore, a systematic degradation pathway was predicted and deduced based on Fukui indices and liquid chromatography-mass spectrometry data. This study presents a paradigm for the application of composite photocatalysts containing substituted phthalocyanines in the degradation of organic wastewater.

A Computation-Guided Design of Highly Defined and Dense Bimetallic Active Sites on a Two-Dimensional Conductive Metal-Organic Framework for Efficient H2O2 Electrosynthesis.

Electrochemical synthesis of hydrogen peroxide (H2O2) via the two-electron oxygen reduction reaction (2e--ORR) provides an alternative method to the energy-intensive anthraquinone method. Metal macrocycles with precise coordination are widely used for 2e--ORR electrocatalysis, but they have to be commonly loaded on conductive substrates, thus exposing a large number of 2e--ORR-inactive sites that result in poor H2O2 production rate and efficiency. Herein, guided by first-principle predictions, a substrate-free and two-dimensional conductive metal-organic framework (Ni-TCPP(Co)), composed of CoN4 sites in porphine(Co) centers and Ni2O8 nodes, is designed as a multi-site catalyst for H2O2 electrosynthesis. The approperiate distance between the CoN4 and Ni2O8 sites in Ni-TCPP(Co) weakens the electron transfer between them, thus ensuring their inherent activities and creating high-density active sites. Meanwhile, the intrinsic electronic conductivity and porosity of Ni-TCPP(Co) further facilitate rapid reaction kinetics. Therefore, outstanding 2e--ORR electrocatalytic performance has been achieved in both alkaline and neutral electrolytes (>90 %/85 % H2O2 selectivity within 0-0.8 V vs. RHE and >18.2/18.0 mol g-1 h-1 H2O2 yield under alkaline/neutral conditions), with confirmed feasibility for water purification and disinfection applications. This strategy thus provides a new avenue for designing catalysts with precise coordination and high-density active sites, promoting high-efficiency electrosynthesis of H2O2 and beyond.

A Computation‐Guided Design of Highly Defined and Dense Bimetallic Active Sites on a Two‐Dimensional Conductive Metal–Organic Framework for Efficient H2O2 Electrosynthesis

AbstractElectrochemical synthesis of hydrogen peroxide (H2O2) via the two‐electron oxygen reduction reaction (2e−‐ORR) provides an alternative method to the energy‐intensive anthraquinone method. Metal macrocycles with precise coordination are widely used for 2e−‐ORR electrocatalysis, but they have to be commonly loaded on conductive substrates, thus exposing a large number of 2e−‐ORR‐inactive sites that result in poor H2O2 production rate and efficiency. Herein, guided by first‐principle predictions, a substrate‐free and two‐dimensional conductive metal–organic framework (Ni‐TCPP(Co)), composed of CoN4 sites in porphine(Co) centers and Ni2O8 nodes, is designed as a multi‐site catalyst for H2O2 electrosynthesis. The approperiate distance between the CoN4 and Ni2O8 sites in Ni‐TCPP(Co) weakens the electron transfer between them, thus ensuring their inherent activities and creating high‐density active sites. Meanwhile, the intrinsic electronic conductivity and porosity of Ni‐TCPP(Co) further facilitate rapid reaction kinetics. Therefore, outstanding 2e−‐ORR electrocatalytic performance has been achieved in both alkaline and neutral electrolytes (>90 %/85 % H2O2 selectivity within 0–0.8 V vs. RHE and >18.2/18.0 mol g−1 h−1 H2O2 yield under alkaline/neutral conditions), with confirmed feasibility for water purification and disinfection applications. This strategy thus provides a new avenue for designing catalysts with precise coordination and high‐density active sites, promoting high‐efficiency electrosynthesis of H2O2 and beyond.

Single-Atom Co-N4 Sites Mediate C=N Formation via Reductive Coupling of Nitroarenes with Alcohols.

It remains challenging to construct C=N bonds due to their facile hydrogenation. Herein, a single Co atom catalyst was discovered to be active for the selective construction of C=N bonds toward the synthesis of imines and N-heterocycles via reductive coupling of nitroarenes with various alcohols, including inert aliphatic ones. DFT calculations and experimental data revealed that the transfer hydrogenation proceeded via the intramolecular hydride transfer and the transfer of H from the α-Csp3-H bond to the nitro group was the rate-determining step. The single Co atoms served as a bridge to transfer the electrons from the catalyst to the adsorbed alcohol molecules, resulting in the activation of the α-Csp3-H bond. Unlike metal nanoparticles, the C=N bonds in imine products can be reserved due to the large steric hindrance from substituents on C and N. DFT calculation also confirmed that transfer hydrogenation of the C=N bonds in imines is thermodynamically unfavored with a much higher energy barrier compared with the transfer hydrogenation of the -NO2 group (1.47 vs 1.15 eV).

Synergistic effects of Co/Fe bimetallic polymer catalysts for enhanced ORR/OER: Insights from thermodynamic and in-situ kinetic study

Bifunctional catalysts for oxygen reduction reaction and oxygen evolution reaction in Zinc-air batteries have been long pursued for the development of clean energy transformation devices. Yet, the underlying mechanism of the promoted electrocatalytic performance is still vague. Herein, a pyrolysis-free Co/Fe bimetallic phthalocyanine coordination polymer Co/Fe-TPDA-CP is firstly synthesized using heterometal tetra-aminophthalocyanines (MTAPcs, M=Co/Fe) as structural model and N,N,N’,N’-tetra(4-folmylphenyl)-p-phenylenediamine (TPDA) as linker. The Co/Fe-TPDA-CP exhibits the high oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities with low ΔE of 692 mV, superior to monometallic Fe-TPDA-CP and Co-TPDA-CP polymers. Density functional theory (DFT) calculation and thermodynamic analysis find that ORR and OER happened separately on Fe and Co sites, in which the presence of second metal modulates the d-band center and optimizes the intermediates adsorption, thereby improving the ORR/OER synergistically. Moreover, dynamic analysis explains that the enhanced ORR stability originated from the fast H2O2 decomposition catalyzed by Co-N4 sites. Furthermore, the Zn-air battery with Co/Fe-TPDA-CP electrode also exhibits a high peak power density (97 mW cm−2) and specific capacity (780 mA h g−1). Through the proof-of-concept bifunctional electrocatalyst with clear structure and synergistic mechanism, this work paves the way for future molecular oxygen electrocatalyst design.

Tailoring Single-Atom Coordination Environments in Carbon Nanofibers via Flash Heating for Highly Efficient Bifunctional Oxygen Electrocatalysis.

The rational design of carbon-supported transition metal single-atom catalysts necessitates precise atomic positioning within the precursor. However, structural collapse during pyrolysis can occlude single atoms, posing significant challenges in controlling both their utilization and coordination environment. Herein, we present a surface atom adsorption-flash heating (FH) strategy, which ensures that the pre-designed carbon nanofiber structure remains intact during heating, preventing unforeseen collapse effects and enabling the formation of metal atoms in nano-environments with either tetra-nitrogen or penta-nitrogen coordination at different flash heating temperatures. Theoretical calculations and in situ Raman spectroscopy reveal that penta-nitrogen coordinated cobalt atoms (Co-N5) promote a lower energy pathway for oxygen reduction and oxygen evolution reactions compared to the commonly formed Co-N4 sites. This strategy ensures that Co-N5 sites are fully exposed on the surface, achieving exceptionally high atomic utilization. The turnover frequency (65.33 s-1) is 47.4 times higher than that of 20 % Pt/C under alkaline conditions. The porous, flexible carbon nanofibers significantly enhance zinc-air battery performance, with a high peak power density (273.8 mW cm-2), large specific capacity (784.2 mAh g-1), and long-term cycling stability over 600 h. Additionally, the flexible fiber-shaped zinc-air battery can power wearable devices, demonstrating significant potential in flexible electronics applications.

Stabilizing atomic Co on 2D ordered mesoporous carbon sandwiched MXene for peroxymonosulfate activation: Enhanced performance and electron-transfer mechanism

In this study, a dual-carrier catalyst is designed for efficient Fenton-like catalysis following non-radical electron-transfer process (ETP). By using 2D mesoporous carbon sandwiched MXene (MCSMx) nanosheets as dual functional substrates, Co single atoms (Co-SA) were confined within MCSMx (CoSA/MCSMx), in which the coordinated Co-N4 sites in highly ordered mesoporous channels (∼10 nm) facilitated the adsorption of peroxymonosulfate (PMS), while the excellent conductivity of MXene as the substrate enhanced the transport of electron. The unique design of Co-SA anchored on dual carriers endows the CoSA/MCSMx with excellent PMS adsorption and rapid electron transfer, achieved nearly 100 % ETP pathway for bisphenol A (BPA) removal and highly selective degradation towards electron-rich pollutants. Moreover, the ETP-induced polymerization transfer reaction of BPA was discovered in the catalytic system, resulting in total organic carbon (TOC) removal ratios of up to 72 %. This work provides new insights into the rational design ETP-based systems for the efficient removal of organic pollutants.

A Generalized Coordination Engineering Strategy for Single-Atom Catalysts toward Efficient Hydrogen Peroxide Electrosynthesis.

Designing non-noble metal single-atom catalysts (M-SACs) for two-electron oxygen reduction reaction (2e-ORR) is attractive for the hydrogen peroxide (H2O2) electrosynthesis, in which the coordination configuration of the M-SACs essentially affects the reaction activity and product selectivity. Though extensively investigated, a generalized coordination engineering strategy has not yet been proposed, which fundamentally hinders the rational design of M-SACs with optimized catalytic capabilities. Herein, a generalized coordination engineering strategy is proposed for M-SACs toward H2O2 electrosynthesis via introducing heteroatoms (e.g., oxygen or sulfur atoms) with higher or lower electronegativity than nitrogen atoms into the first sphere of metal-N4 system to tailor their electronic structure and adjust the adsorption strength for *OOH intermediates, respectively, thus optimizing their electrocatalytic capability for 2e-ORR. Specifically, the (O, N)-coordinated Co SAC (Co-N3O) and (S, N)-coordinated Ni SAC (Ni-N3S) are precisely synthesized, and both present superior 2e-ORR activity (Eonset: ≈0.80V versus RHE) and selectivity (≈90%) in alkaline conditions compared with conventional Co-N4 and Ni-N4 sites. The high H2O2 yield rates of 14.2 and 17.5moLg-1h-1 and long-term stability over 12h are respectively achieved for Co-N3O and Ni-N3S. Such favorable 2e-ORR pathway of the catalysts is also theoretically confirmed by the kinetics simulations.

Built-in electric field mediated S-scheme charge migration and Co-N4(II) sites in cobalt phthalocyanine/MIL-68(In)-NH2 heterojunction for boosting photocatalytic nitric oxide oxidation

The efficiency of photocatalytic Nitric Oxide(NO) oxidation is limited by the lack of oxygen(O2) active sites and poor charge carrier separation. To address this challenge, we developed a molecular Cobalt Phthalocyanine modified MIL-68(In)–NH2 photocatalyst with a robust Built-in electric field(BIEF). In the 2 % CoPc-MIN sample, the BIEF strength is increased by 3.54 times and 5.83 times compared to pristine CoPc and MIL-68(In)–NH2, respectively. This BIEF facilitates the efficient S-scheme charge transfer, thereby enhancing photogenerated carrier separation. Additionally, the Co-N4(II) sites in CoPc can effectively trap the separated photoexcited electrons in the S-scheme system. In addition, the Co-N4(II) sites can also serve as active sites for O2 adsorption and activation, promoting the generation of superoxide radical (O2–), thereby driving the direct conversion of NO to nitrate(NO3–). Consequently, the 2 % CoPc-MIN sample exhibits a remarkable photocatalytic NO removal efficiency of 79.37 % while effectively suppressing the formation of harmful by-product nitrogen dioxide(NO2) to below 3.5 ppb. This study provides a feasible strategy for designing high-efficiency O2 activation photocatalysts for NO oxidation.

Design of Atomically Dispersed CoN4 Sites and Co Clusters for Synergistically Enhanced Oxygen Reduction Electrocatalysis.

Constructing dual-site catalysts consisting of atomically dispersed metal single atoms and metal atomic clusters (MACs) is a promising approach to further boost the catalytic activity for oxygen reduction reaction (ORR). Herein, a porous CoSA-AC@SNC featuring the coexistence of Co single-atom sites (CoN4) and S-coordinated Co atomic clusters (SCo6) in S, N co-doped carbon substrate is successfully synthesized by using porphyrinic metal-organic framework (Co-TPyP MOF) as the precursor. The introduction of the sulfur source creates abundant microstructural defects to anchor Co metal clusters, thus modulating the electronic structure of its surrounding carbon substrate. The synergistic effect between the two types of active sites and structural advantages, in turn, results in high ORR performance of CoSA-AC@SNC with half-wave potential (E1/2) of 0.86V and Tafel slope of 50.17mVdec-1. Density functional theory (DFT) calculations also support the synergistic effect between CoN4 and SCo6 by detailing the catalytic mechanism for the improved ORR performance. The as-fabricated Zn-air battery (ZAB) using CoSA-AC@SNC demonstrates impressive peak power density of 174.1mWcm-2 and charge/discharge durability for 148h. This work provides a facile synthesis route for dual-site catalysts and can be extended to the development of other efficient atomically dispersed metal-based electrocatalysts.

Concave single-atom Co nanozymes with densely edge-hosted active sites for highly sensitive immunoassay

Regulating the geometric and electronic structures of single-atom catalysts could promote the potential to improve their enzyme-like catalytic performance. Herein, we demonstrate that concave single-atom Co catalysts with edge-hosted and dense active Co-N4 sites incorporated in nitrogen-doped hierarchical porous carbon (H-Co SACs) can act as highly efficient oxidase mimics. In particular, the engineered H-Co SACs with dense active Co-N4 moieties in the edge sites were found to display 3.1 times higher catalytic activity than that of traditional intact Co single-atom catalysts (L-Co SACs). Combined experimental and theoretical simulations reveal that the geometric structure and the interactions between adjacent edge-hosted CoN4 sites synergistically affect the electronic structure of the Co single-atom nanozymes, resulting in strong oxygen adsorption/activation and low energy barrier of the rate-determining step (RDS) in the reaction process, which are demonstrated be more beneficial for the oxidase-like catalytic performance. As a proof-of-concept application, the H-Co SACs were applied to the colorimetric enzyme-linked immunosorbent assay (ELISA) of neuron specific enolase (NSE) with a detection limit of 5.19 pg/ mL, outperforming both the intact Co single-atom catalysts and standard commercial ELISA kits. The present study could not only highlight the significance of geometric structure and active sites density effect on their enzyme-like catalytic efficiency, but also broaden their practical clinical application range of nanozymes at the atomic level.

Overcome the trade-off in electro-fenton chemistry for in situ H2O2 generation-activation by tandem CoFe bimetallic single-atom configuration

Dual-atomic catalysts (DACs) demonstrated remarkable potential in addressing key challenges in electro-Fenton (EF) processes. In this study, we synthesized an EF DACs comprising both CoN4 and FeN4 sites, which was achieved a high H2O2 generation rate (1.68 mM−1h−1) and 100 % bisphenol A degradation efficiency via successive two-electron oxygen reduction and one-electron Fenton reactions (2e− ORR + 1e− Fenton). Our findings indicated that the single-atom nitrogen coordination of CoN4 and FeN4 sites plays crucial roles in regulating the adsorption of key intermediates of *OOH and *H2O2. The bimetallic sites independently regulated the binding energies of *OOH on CoN4 (pyrrole-type) for favorable H2O2 generation and its subsequent activation on adjacent FeN4 (pyridine-type). Thus, the dual-site engineering addresses the trade-off of in situ H2O2 generation-activation in EF chemistry, realizing high electron utilization efficiency and fast pollutant degradation toward efficient and sustainable water treatment.

Locally Curved Surface with CoN4 Sites Enables Hard Carbon with Superior Sodium‐Ion Storage Performances at −40 °C

AbstractThe impressive electrochemical performance of sodium‐ion batteries at low temperatures has long been recognized as a promising technical advantage. However, the inadequate transport kinetics of Na+ ions and complex interfacial reactions at the hard carbon anode surface hinder the practical implementation of commercial sodium‐ion batteries. Herein, a novel approach to address this issue by introducing a homogenized functional carbon coating layer with a locally curved configuration is proposed. This coating layer is designed to accommodate single CoN4 sites on the surface of commercial hard carbon particles, resulting in enhanced sodium storage performance at low temperatures. The surface‐modified hard carbon anode material (HC‐Z1) demonstrates a commendable rate performance of 220.6 mAh g−1 at 3 A g−1@25 °C and a substantial reversible capacity of 288.7 mAh g−1 with an 89% capacity retention at 0.06 A g−1@‐20 °C. Furthermore, even at a temperature as low as −40 °C, the reversible capacity remains at 270 mAh g−1 at 0.06 A g−1. Extensive characterizations and theoretical calculations provide evidence that the optimized interface between the electrode and electrolyte effectively enhances the desolvation and migration of Na+ ions, particularly at low temperatures.

Improved oxygen electrocatalysis at FeN4 and CoN4 sites via construction of axial coordination

Improved oxygen electrocatalysis at FeN4 and CoN4 sites via construction of axial coordination

Theoretical study of electrochemical hydrogen evolution reaction of Pt–Co diatomic sites catalyst

Hydrolytic Hydrogen is a clean hydrogen production method. To mitigate the substantial costs associated with water electrolysis, electrocatalysts are crucial in decreasing the cathodic reaction involved in hydrogen hydrolysis, specifically, the overpotential for hydrogen evolution reaction (HER). Compared to traditional catalysts and single-atom catalysts, Pt–Co diatomic sites catalyst exhibit excellent hydrogen evolution reaction activity and stability. We have established eight different structures of dual-center metal catalysts based on graphene planes. A systematic study was conducted on the catalytic performance and mechanism of these configurations, among which the structure with the best hydrogen evolution reaction activity was CoN4/PtC2N2, with a Gibbs free energy (ΔG) of 0.004 eV. Electronic structure analysis confirms that H follows the Sabatier mechanism on diatomic catalysts, and the catalyst exhibits excellent HER performance for moderate adsorption strength of H atoms. The d-band centers of Co and Pt atoms in the electrocatalyst CoN4–PtC2N2 are lower than those of a single system, indicating that the electronic effect between the CoN4 and PtC2N2 sites can enhance the inherent HER activity of the catalyst. This study expands the application scope of dual-site catalysts and provides new insights for the design and synthesis of dual-site hydrogen evolution catalysts.

Tailored Local Electronic Environment of Co-N4 Sites in Cobalt Phthalocyanines for Enhanced CO2 Reduction Reaction.

Atomically dispersed Co-N4-based catalysts have been recently emerging as one of the most promising candidates for facilitating CO2 reduction reaction (CO2RR). The local electronic environment of Co-N4 sites in these catalysts is considered to play a critical role in adjusting the catalytic performance, the effort of which however is not yet clearly verified. Herein, a series of cobalt phthalocyanines with different peripheral substituents including unsubstituted phthalocyanine Co(II) (CoPc), 2,9,16,23-tetramethoxyphthalocyaninato Co(II) (CoPc-4OCH3), and 2,9,16,23-tetranitrophthalocyaninato Co(II) (CoPc-4NO2) are supported onto the surface of the multi-walled carbon nanotubes (CNTs), affording CoPc@CNTs, CoPc-4OCH3@CNTs, and CoPc-4NO2@CNTs. X-ray photoelectron spectroscopy and X-ray absorption near-edge structure measurements disclose the influence of the peripheral substituents on the local electronic structure of Co atoms in these three catalysts. Electrochemical tests indicate the higher CO2RR performance of CoPc-4OCH3@CNTs compared to CoPc@CNTs and CoPc-4NO2@CNTs as exemplified by the higher Faraday efficiency of CO, larger part current densities, and better stability displayed by CoPc-4OCH3@CNTs at the applied voltage range from -0.6 to -1.0V versus RHE in both H-cell and flow cell. These results highlight the effect of the electron-donating -OCH3 substituent on the enhanced catalytic activity of CoPc-4OCH3@CNTs, which will help develop Co-N4-based catalysts with promising catalytic performance toward CO2RR.

Co-NC catalyst with rich coordinated nitrogen and hierarchical porous structure for oxygen reduction reaction

Cobalt nitrogen-doped carbon (Co-NC) catalysts are synthesized for oxygen reduction reaction (ORR) via the pyrolysis of zinc-mediated and SiO2-templated 2,6-diaminopyridine (DAP) composites. The resulting Co-NC(Zn12-SiO2[20])-900 demonstrates exceptional ORR activities, with half-wave and onset potentials of 0.835 V and 0.875 V, respectively, which is similar to Pt/C catalyst. In long-term durability test, the Co-NC(Zn12-SiO2[20])-900 catalyst exhibits a negligible E1/2 shift, and in methanol tolerance tests, it displays significantly better performance than commercial Pt/C catalyst. The superior performance can be attributed to the hierarchical porous structure, dense and highly accessible Co-N4 and graphitic nitrogen (g-N) sites. The high content of Co-N4 and g-N sites enhances 3d-orbital filling and reduces the Co centers' on-site magnetic moment, as calculated by density functional theory. This may lead to a decrease in the energy barrier of the rate-determining step (RDS), which in turn enhances the intrinsic activity of the ORR.

Hydrophilic phthalocyanine covalent organic frameworks for enhanced electrocatalytic H2O2 production

The electrocatalytic 2e− oxygen reduction reaction (ORR) is considered as a promising pathway to replace conditional anthraquinone process for hydrogen peroxide (H2O2) manufacture. However, the efficient electrocatalysts towards 2e− ORR remain urgently desired. Herein, hydrophilic two-dimensional cobalt phthalocyanine (CoPc) covalent organic frameworks (COFs), denoted as CoPc-2SO3H-COF and CoPc-SO3H-COF, were afforded via the imidization reaction of 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato cobalt(II) with hydrophilic building blocks 2,5-diaminobenzenesulfonic acid and 1,4-benzenedisulfonic acid, respectively. Powder X-ray diffraction, transmission electron microscope, and N2 sorption experiment results reveal the crystalline and porous structure of these two COFs. Moreover, the water contact angle and proton conduction measurements demonstrate the hydrophilic properties of these two COFs owing to the introduction of −SO3H into their skeleton. This, in combination with the high-efficiency active Co-N4 sites towards 2e− ORR, endows these two COFs with enhanced 2e− ORR activity in the aqueous electrolyte. In particular, CoPc-2SO3H-COF exhibits outstanding electrocatalytic H2O2 production performance with a stable H2O2 selectivity of 88.3 % under a high current density of 125 mA cm−2 for 20 h in a flow cell.

Single-Atomic Co-N4 Sites with CrCo Nanoparticles for Metal-Air Battery-Driven Hydrogen Evolution.

Designing highly active and robust earth abundant trifunctional electrocatalysts for energy storage and conversion applications remain an enormous challenge. Herein, we report a trifunctional electrocatalyst (CrCo/CoN4@CNT-5), synthesized at low calcination temperature (550 °C), which consists of Co-N4 single atom and CrCo alloy nanoparticles and exhibits outstanding electrocatalytic performance for the hydrogen evolution reaction, oxygen evolution reaction, and oxygen reduction reaction. The catalyst is able to deliver a current density of 10 mA cm-2 in an alkaline electrolytic cell at a very low cell voltage of ∼1.60 V. When the catalyst is equipped in a liquid rechargeable Zn-air battery, it endowed a high open-circuit voltage with excellent cycling durability and outperformed the commercial Pt/C+IrO2 catalytic system. Furthermore, the Zn-air battery powered self-driven water splitting system is displayed using CrCo/CoN4@CNT-5 as sole trifunctional catalyst, delivering a high H2 evolution rate of 168 μmol h-1. Theoretical calculations reveal synergistic interaction between Co-N4 active sites and CrCo nanoparticles, favoring the Gibbs free energy for H2 evolution. The presence of Cr not only enhances the H2O adsorption and dissociation but also tunes the electronic property of CrCo nanoparticles to provide optimized hydrogen binding capacity to Co-N4 sites, thus giving rise to accelerated H2 evolution kinetics. This work highlights the importance of the presence of small quantity of Cr in enhancing the electrocatalytic activity as well as robustness of single-atom catalyst and suggests the design of the multifunctional robust electrocatalysts for long-term H2 evolution application.

Atomically dispersed Co-N4 to activate peroxymonosulfate for efficient atrazine degradation: Synergistic radical and non-radical ways

Cobalt based nanomaterials are widely employed as effective catalysts for peroxymonosulfate (PMS) activation in advanced oxidation processes (AOPs). Single atom catalysts (SACs) are state-of-the-art materials that endow active metal sites with maximal exposure to the reactants. In this study, molybdenum disulfide nanospheres with a crumpled surface (cnMoS2) were designed and synthesized to decorate atomically dispersed Co-N4 sites by immobilizing Co in its unique surface fold structure with a nitrogen/carbon coating. The resulting Co-N-C-cnMoS2 catalysts were used to activate PMS for rapid degradation of atrazine (ATZ). The Co-N4 sites were considered to be the main active sites, enabling the optimal 4.8Co-N-C-cnMoS2 catalyst to remove 100 % of ATZ within 20 min. In addition, 4.8Co-N-C-cnMoS2 catalyst also showed good durability, tolerance to inorganic anions and cations, and high activity in a wide pH range. The cnMoS2 provided a platform to hold atomically Co-N4 sites, played the degradation roles though it was secondary, and moreover accelerated Co2+/Co3+ cycles. In the 4.8Co-N-C-cnMoS2/PMS system, sulfate radical (SO4• ‾), hydroxyl radicals (•OH), superoxide radical (O2• ‾) and singlet oxygen (1O2) were generated, among which SO4• ‾ and 1O2 were the predominant active substances triggering the ATZ degradation.