Atomically dispersed nanozymes have garnered immense attention within the biomedical field,while precisely designing these nanozymes and elucidating their intricate structure-performance relationships of their structu...Atomically dispersed nanozymes have garnered immense attention within the biomedical field,while precisely designing these nanozymes and elucidating their intricate structure-performance relationships of their structures and antibacterial performance remain the formidable challenges.Herein,we fabricated defect-rich graphene supported layered Ir cluster nanozymes for antibacterial applications.Steady-state kinetic experiments revealed that the layered Ir clusters exhibited the higher catalytic efficiency of 1.16 mM^(−1)·s^(−1)with 3,3′,5,5′-tetramethylbenzidine(TMB)and 0.18 mM^(−1)·s^(−1)with H_(2)O_(2),compared to Ir nanoparticle(0.55 and 0.1 mM^(−1)·s^(−1))and the atomically dispersed Ir single-atom nanozyme(SAzyme)(0.3 and 0.039 mM^(−1)·s^(−1))and other previously reported single-atom nanozymes.Moreover,both experimental results and density functional theory studies disclosed that the layered Ir clusters exhibited the enhanced ability to facilitate the conversion of hydrogen peroxide into hydroxyl free radicals,signifying the higher catalytic efficiency than that on Ir nanoparticles and Ir single-atoms.Notably,the Ir cluster nanozyme with robust peroxidase-like activity had 100%antimicrobial rate against E.coli and S.aureus,underscoring its potential applications in antibacterial fields.展开更多
Developing cost-effective and highly efficient oxygen evolution reaction(OER)electrocatalysts that operate in both acidic and alkaline media is crucial for indus-trial electrocatalytic water splitting.However,achievin...Developing cost-effective and highly efficient oxygen evolution reaction(OER)electrocatalysts that operate in both acidic and alkaline media is crucial for indus-trial electrocatalytic water splitting.However,achieving high performance under dual pH conditions remains a significant challenge.Herein,we report the synthe-sis of multi-sized RuO_(2)sub-nanoclusters on Co_(3)O_(4)nanoarrays via a facile method,which demonstrates exceptional OER activity in both acidic and alkaline environ-ments.The optimized catalyst exhibits remarkably low overpotentials of 165 mV in 0.5 M H_(2)SO_(4)and 223 mV in 1 M KOH at a current density of 10 mA cm^(-2),respectively.Additionally,it exhibits outstanding stability,maintaining perfor-mance over a 10-h continuous operation,which is attributed to the robust struc-tural stability of the dispersed RuO_(2)sub-nanocluster morphology.Atomic-scale investigations reveal a layer-by-layer growth mechanism of Ru on the Co_(3)O_(4)sub-strate,transitioning from single atoms to monolayer clusters and ultimately to sub-nanoclusters as Ru loading increases.This growth mechanism provides a rational strategy for the precise design and synthesis of advanced cluster-based cat-alysts.Density functional theory(DFT)calculations further elucidate the strong oxide-support interactions between RuO_(2)clusters and the Co_(3)O_(4)matrix,facilitat-ing electron transfer from RuO_(2)to Co_(3)O_(4)and generating an electron-deficient region.This electronic modulation enhances–OH adsorption and accelerates OER kinetics.These findings underscore the potential of metal sub-nanoclusters for designing highly efficient and durable electrocatalysts for water electrolysis.展开更多
As a new water treatment technology,Fenton-like reaction has great potential.In this study,we successfully prepared an excellent Fenton-like catalyst,which is composed of cobalt monoatoms and asymmetric subnanocluster...As a new water treatment technology,Fenton-like reaction has great potential.In this study,we successfully prepared an excellent Fenton-like catalyst,which is composed of cobalt monoatoms and asymmetric subnanoclusters(labeled CoSA/Clu-C_(2)N),and exhibits excellent peroxymonosulfate(PMS)activation reactivity.By directly comparing the catalytic properties of CoSA-C_(2)N and CoSA/Clu-C_(2)N,the synergistic effects of coasymmetric Co subclusters and Co atoms on the activation of PMS and degradation of organic micropollutants were investigated.The results showed that CoSA/Clu-C_(2)N had higher degradation rates of carbamazepine(CBZ),antipyrine(AT)and chlorobenzoic acid(CA)when combined with active oxidant PMS.The cyclic frequency of CBZ was 5.4 min^(-1),which was twice as high as the catalytic constant of CoSA-C_(2)N(2.4 min^(-1)).The results show that CoSA/Clu-C_(2)N cobalt subnanoclusters and cobalt single atom can synergistically improve the catalytic performance of activated PMS oxidation of micropollutants in water.In addition,electron paramagnetic resonance(EPR)technology has proved that the introduction of Co subnano clusters in CoSA/Clu-C_(2)N is conducive to the production of singlet oxygen(1O_(2)),thereby improving the efficiency of pollutant oxidation.This work lays a solid foundation for the future design of advanced multifunctional catalysts by carefully regulating and combining monmetallic atoms and metal subnanoclusters.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22072162,U21B2092,22402210,22202213,and 21961160722)International Partnership Program of Chinese Academy of Sciences(No.172GJHZ2022028MI)+2 种基金Shenyang Young Talents Program(No.RC220155)Natural Science Foundation of Liaoning Province(No.2024-MS-05)Liaoning BaiQianWan Talents Program and Guangxi Collaborative Innovation Centre of Structure and Property for New Energy and Materials,Science Research,Technology Development Project of Guilin(No.20210102-4)。
文摘Atomically dispersed nanozymes have garnered immense attention within the biomedical field,while precisely designing these nanozymes and elucidating their intricate structure-performance relationships of their structures and antibacterial performance remain the formidable challenges.Herein,we fabricated defect-rich graphene supported layered Ir cluster nanozymes for antibacterial applications.Steady-state kinetic experiments revealed that the layered Ir clusters exhibited the higher catalytic efficiency of 1.16 mM^(−1)·s^(−1)with 3,3′,5,5′-tetramethylbenzidine(TMB)and 0.18 mM^(−1)·s^(−1)with H_(2)O_(2),compared to Ir nanoparticle(0.55 and 0.1 mM^(−1)·s^(−1))and the atomically dispersed Ir single-atom nanozyme(SAzyme)(0.3 and 0.039 mM^(−1)·s^(−1))and other previously reported single-atom nanozymes.Moreover,both experimental results and density functional theory studies disclosed that the layered Ir clusters exhibited the enhanced ability to facilitate the conversion of hydrogen peroxide into hydroxyl free radicals,signifying the higher catalytic efficiency than that on Ir nanoparticles and Ir single-atoms.Notably,the Ir cluster nanozyme with robust peroxidase-like activity had 100%antimicrobial rate against E.coli and S.aureus,underscoring its potential applications in antibacterial fields.
基金NSFC,Grant/Award Number:52203304Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory,Grant/Award Numbers:XHD2022-001,XHD2021-001,XHQN2022-005,XHRD2023-005Guangdong Basic and Applied Basic Research Foundation,Grant/Award Number:2022A1515110627。
文摘Developing cost-effective and highly efficient oxygen evolution reaction(OER)electrocatalysts that operate in both acidic and alkaline media is crucial for indus-trial electrocatalytic water splitting.However,achieving high performance under dual pH conditions remains a significant challenge.Herein,we report the synthe-sis of multi-sized RuO_(2)sub-nanoclusters on Co_(3)O_(4)nanoarrays via a facile method,which demonstrates exceptional OER activity in both acidic and alkaline environ-ments.The optimized catalyst exhibits remarkably low overpotentials of 165 mV in 0.5 M H_(2)SO_(4)and 223 mV in 1 M KOH at a current density of 10 mA cm^(-2),respectively.Additionally,it exhibits outstanding stability,maintaining perfor-mance over a 10-h continuous operation,which is attributed to the robust struc-tural stability of the dispersed RuO_(2)sub-nanocluster morphology.Atomic-scale investigations reveal a layer-by-layer growth mechanism of Ru on the Co_(3)O_(4)sub-strate,transitioning from single atoms to monolayer clusters and ultimately to sub-nanoclusters as Ru loading increases.This growth mechanism provides a rational strategy for the precise design and synthesis of advanced cluster-based cat-alysts.Density functional theory(DFT)calculations further elucidate the strong oxide-support interactions between RuO_(2)clusters and the Co_(3)O_(4)matrix,facilitat-ing electron transfer from RuO_(2)to Co_(3)O_(4)and generating an electron-deficient region.This electronic modulation enhances–OH adsorption and accelerates OER kinetics.These findings underscore the potential of metal sub-nanoclusters for designing highly efficient and durable electrocatalysts for water electrolysis.
基金supported by the National Natural Science Foundation of China(No.22375019).
文摘As a new water treatment technology,Fenton-like reaction has great potential.In this study,we successfully prepared an excellent Fenton-like catalyst,which is composed of cobalt monoatoms and asymmetric subnanoclusters(labeled CoSA/Clu-C_(2)N),and exhibits excellent peroxymonosulfate(PMS)activation reactivity.By directly comparing the catalytic properties of CoSA-C_(2)N and CoSA/Clu-C_(2)N,the synergistic effects of coasymmetric Co subclusters and Co atoms on the activation of PMS and degradation of organic micropollutants were investigated.The results showed that CoSA/Clu-C_(2)N had higher degradation rates of carbamazepine(CBZ),antipyrine(AT)and chlorobenzoic acid(CA)when combined with active oxidant PMS.The cyclic frequency of CBZ was 5.4 min^(-1),which was twice as high as the catalytic constant of CoSA-C_(2)N(2.4 min^(-1)).The results show that CoSA/Clu-C_(2)N cobalt subnanoclusters and cobalt single atom can synergistically improve the catalytic performance of activated PMS oxidation of micropollutants in water.In addition,electron paramagnetic resonance(EPR)technology has proved that the introduction of Co subnano clusters in CoSA/Clu-C_(2)N is conducive to the production of singlet oxygen(1O_(2)),thereby improving the efficiency of pollutant oxidation.This work lays a solid foundation for the future design of advanced multifunctional catalysts by carefully regulating and combining monmetallic atoms and metal subnanoclusters.
