Besides the pandemic caused by the coronavirus outbreak, many other pathogenic microbes also pose a devastating threat to human health, for instance, pathogenic bacteria. Due to the lack of ...broad‐spectrum antibiotics, it is urgent to develop nonantibiotic strategies to fight bacteria. Herein, inspired by the localized “capture and killing” action of bacteriophages, a virus‐like peroxidase‐mimic (V‐POD‐M) is synthesized for efficient bacterial capture (mesoporous spiky structures) and synergistic catalytic sterilization (metal–organic‐framework‐derived catalytic core). Experimental and theoretical calculations show that the active compound, MoO3, can serve as a peroxo‐complex‐intermediate to reduce the free energy for catalyzing H2O2, which mainly benefits the generation of •OH radicals. The unique virus‐like spikes endow the V‐POD‐M with fast bacterial capture and killing abilities (nearly 100% at 16 µg mL–1). Furthermore, the in vivo experiments show that V‐POD‐M possesses similar disinfection treatment and wound skin recovery efficiencies to vancomycin. It is suggested that this inexpensive, durable, and highly reactive oxygen species (ROS) catalytic active V‐POD‐M provides a promising broad‐spectrum therapy for nonantibiotic disinfection.
A bioinspired, spiky, and highly catalytic‐active virus‐like peroxidase‐mimic (V‐POD‐M) is synthesized for the localized “capture and killing” eradication of pathogenic bacteria. Experimental and theoretical calculations demonstrate that the V‐POD‐M exhibits strong bacterial interactions and efficient capture, synergistic catalytic sterilization, and similar in vivo disinfection efficiency to that of vancomycin, which provides a promising broad‐spectrum therapy for nonantibiotic disinfection.
Exploring highly active, stable electrocatalysts with earth‐abundant metal centers for the oxygen reduction reaction (ORR) is essential for sustainable energy conversion. Due to the high cost and ...scarcity of platinum, it is a general trend to develop metal–N–C (M–N–C) electrocatalysts, especially those prepared from the zeolite imidazolate framework (ZIF) to replace/minimize usage of noble metals in ORR electrocatalysis for their amazingly high catalytic efficiency, great stability, and readily‐tuned electronic structure. In this review, the most pivotal advances in mechanisms leading to declined catalytic performance, synthetic strategies, and design principles in engineering ZIF‐derived M–N–C for efficient ORR catalysis, are presented. Notably, this review focuses on how to improve intrinsic ORR activity, such as M–Nx–Cy coordination structures, doping metal‐free heteroatoms in M–N–C, dual/multi‐metal sites, hydrogen passivation, and edge‐hosted M–Nx. Meanwhile, how to increase active sites density, including formation of M–N complex, spatial confinement effects, and porous structure design, are discussed. Thereafter, challenges and future perspectives of M–N–C are also proposed. The authors believe this instructive review will provide experimental and theoretical guidance for designing future, highly active ORR electrocatalysts, and facilitate their applications in diverse ORR‐related energy technologies.
Recent advances in designing ZIF‐derived atomic metal–N–C electrocatalysts for the oxygen reduction reaction are presented. The authors present the most pivotal advances, synthetic strategies, and performance decline mechanisms; design principles for improving the intrinsic ORR activity and increasing the number of active sites are systematically discussed. The challenges and future perspectives of metal–N–C electrocatalysts are also highlighted.
Benefiting from the merits of low cost, ultrahigh‐energy densities, and environmentally friendliness, metal–sulfur batteries (M–S batteries) have drawn massive attention recently. However, their ...practical utilization is impeded by the shuttle effect and slow redox process of polysulfide. To solve these problems, enormous creative approaches have been employed to engineer new electrocatalytic materials to relieve the shuttle effect and promote the catalytic kinetics of polysulfides. In this review, recent advances on designing principles and active centers for polysulfide catalytic materials are systematically summarized. At first, the currently reported chemistries and mechanisms for the catalytic conversion of polysulfides are presented in detail. Subsequently, the rational design of polysulfide catalytic materials from catalytic polymers and frameworks to active sites loaded carbons for polysulfide catalysis to accelerate the reaction kinetics is comprehensively discussed. Current breakthroughs are highlighted and directions to guide future primary challenges, perspectives, and innovations are identified. Computational methods serve an ever‐increasing part in pushing forward the active center design. In summary, a cutting‐edge understanding to engineer different polysulfide catalysts is provided, and both experimental and theoretical guidance for optimizing future M–S batteries and many related battery systems are offered.
The recent advances on designing principles and active centers for polysulfide catalytic materials toward M–S batteries are summarized. The reported chemistries and mechanisms, the rational design principles from catalytic polymers and frameworks to active sites loaded carbons, and primary challenges and perspectives are comprehensively discussed, which offers new understanding and guidance for engineering catalytic nanostructures in M–S batteries.
Bioelectronics are powerful tools for monitoring and stimulating biological and biochemical processes, with applications ranging from neural interface simulation to biosensing. The increasing demand ...for bioelectronics has greatly promoted the development of new nanomaterials as detection platforms. Recently, owing to their ultrathin structures and excellent physicochemical properties, emerging two‐dimensional (2D) materials have become one of the most researched areas in the fields of bioelectronics and biosensors. In this timely review, the physicochemical structures of the most representative emerging 2D materials and the design of their nanostructures for engineering high‐performance bioelectronic and biosensing devices are presented. We focus on the structural optimization of emerging 2D material‐based composites to achieve better regulation for enhancing the performance of bioelectronics. Subsequently, the recent developments of emerging 2D materials in bioelectronics, such as neural interface simulation, biomolecular/biomarker detection, and skin sensors are discussed thoroughly. Finally, we provide conclusive views on the current challenges and future perspectives on utilizing emerging 2D materials and their composites for bioelectronics and biosensors. This review will offer important guidance in designing and applying emerging 2D materials in bioelectronics, thus further promoting their prospects in a wide biomedical field.
Emerging two‐dimensional (2D) materials have been studied as fascinating bioelectronics due to their ultrathin structures and excellent physicochemical properties. This review summarizes the structural optimization of them toward bioelectronics and biosensors, which encompasses neural interface simulation, biomolecular/biomarker detection, and skin sensors. Current challenges and future perspectives of utilizing emerging 2D materials and their composites for bioelectronics and biosensors are highlighted.
We synthesized a series of carbon‐supported atomic metal‐N‐C catalysts (M‐SACs: M=Mn, Fe, Co, Ni, Cu) with similar structural and physicochemical properties to uncover their catalytic activity trends ...and mechanisms. The peroxymonosulfate (PMS) catalytic activity trends are Fe‐SAC>Co‐SAC>Mn‐SAC>Ni‐SAC>Cu‐SAC, and Fe‐SAC displays the best single‐site kinetic value (1.65×105 min−1 mol−1) compared to the other metal‐N‐C species. First‐principles calculations indicate that the most reasonable reaction pathway for 1O2 production is PMS→OH*→O*→1O2; M‐SACs that exhibit moderate and near‐average Gibbs free energies in each reaction step have a better catalytic activity, which is the key for the outstanding performance of Fe‐SACs. This study gives the atomic‐scale understanding of fundamental catalytic trends and mechanisms of PMS‐assisted reactive oxygen species production via M‐SACs, thus providing guidance for developing M‐SACs for catalytic organic pollutant degradation.
A series of carbon‐supported atomic metal‐N‐C catalysts with similar structural and physicochemical properties were synthesized to uncover the activity trends and mechanisms in peroxymonosulfate‐assisted reactive oxygen species production. Fe‐SAC displays the best single‐site kinetic value (1.65×105 min−1 mol−1), and the PMS→OH*→O*→1O2 is the most reasonable 1O2 reaction pathway.
To deal with the ever‐growing toxic benzene‐derived compounds in the water system, extensive efforts have been dedicated for catalytic degradation of pollutants. However, the activities and ...efficiencies of the transition metal‐based nanoparticles or single‐atom sites are still ambiguous in Fenton‐like reactions. Herein, to compare the Fenton‐like catalytic efficiencies of the nanoparticles and single atoms, the free‐standing nanofibrous catalyst comprising Co nanocrystals and Co–Nx codoped carbon nanotubes (CNTs) or bare Co–Nx doped CNTs is fabricated. It is noteworthy that all these nanofibrous catalysts exhibit efficient activities, mesoporous structures, and conductive carbon networks, which allow a feasible validation of the catalytic effects. Benefiting from the maximized atomic utilization, the atomic Co–Nx centers exhibit much higher reaction kinetic constant (κ = 0.157 min−1) and mass activity toward the degradation of bisphenol A, far exceeding the Co nanocrystals (κ = 0.082 min−1). However, for the volume activities, the single‐atom catalyst does not show apparent advantages compared to the nanocrystal‐based catalyst. Overall, this work not only provides a viable pathway for comparing Fenton‐like catalytic effects of transition metal‐based nanoparticles or single atoms but also opens up a new avenue for developing prominent catalysts for organic pollutants’ degradation.
The Fenton‐like catalytic activities and efficiencies of Co‐based nanoparticles and single‐atom structures are investigated and compared systematically via engineering catalysts comprising Co‐nanocrystals and atomic Co–Nx codoped carbon nanotubes. Benefiting from the maximized atomic utilization, the atomic Co–Nx centers exhibit much higher reaction kinetic constant and mass activity toward the degradation of bisphenol A, far exceeding the Co nanoparticles.
To deal with the ever-growing toxic benzene-derived compounds in the water system, extensive efforts have been dedicated for catalytic degradation of pollutants. However, the activities and ...efficiencies of the transition metal-based nanoparticles or single-atom sites are still ambiguous in Fenton-like reactions. Herein, to compare the Fenton-like catalytic efficiencies of the nanoparticles and single atoms, the free-standing nanofibrous catalyst comprising Co nanocrystals and Co-N
codoped carbon nanotubes (CNTs) or bare Co-N
doped CNTs is fabricated. It is noteworthy that all these nanofibrous catalysts exhibit efficient activities, mesoporous structures, and conductive carbon networks, which allow a feasible validation of the catalytic effects. Benefiting from the maximized atomic utilization, the atomic Co-N
centers exhibit much higher reaction kinetic constant (κ = 0.157 min
) and mass activity toward the degradation of bisphenol A, far exceeding the Co nanocrystals (κ = 0.082 min
). However, for the volume activities, the single-atom catalyst does not show apparent advantages compared to the nanocrystal-based catalyst. Overall, this work not only provides a viable pathway for comparing Fenton-like catalytic effects of transition metal-based nanoparticles or single atoms but also opens up a new avenue for developing prominent catalysts for organic pollutants' degradation.
The extensive research into developing new nanomedicines during the past few years has witnessed significant progress in diverse biomedical fields, especially for combating drug resistance in ...antitumor and antibacterial therapies. Recently, transition‐metal‐based enzymatic nanoagents (TM‐EnzNAs) with catalytic production of reactive oxygen species (ROS) have been designed and intensively explored, which have become powerful nanoplatforms and exciting research frontiers in constructing next‐generation nanotherapeutics to combat drug‐resistant tumors and bacteria. Here, the focus is on the recent design, fundamental principles, and material chemistries in developing and applications of TM‐EnzNAs. At first, the different ROS‐producing mechanisms and the key factors to enhance ROS level are carefully concluded, and the analytic methods are systematically summarized. Then, the rationally engineered TM‐EnzNAs via different synthetic approaches with high ROS producing efficiencies are comprehensively discussed, especially the catalytic activities, mechanisms, and structure–function relationships. After that, the representative applications of these ROS‐catalytic TM‐EnzNAs for antitumor and bacterial eradication are summarized in detail. Finally, the primary challenges and future perspectives have also been outlined. It is anticipated new therapeutic insights into combating drug‐resistant tumors and bacteria will be provided, and significant new inspiration for designing future enzymatic nanoagents is offered.
Recent advancements in transition‐metal‐based enzymatic nanoagents for reactive oxygen species (ROS) generation have been summarized here. The mechanisms and the key factors to enhance ROS level, analytic methods, rational design, antitumor and antibacterial applications, and primary challenges and future perspectives are carefully outlined, which will offer a cutting‐edge understanding and guidance for the future design of ROS‐catalytic nanostructures.
Nanomaterials‐based artificial enzymes (AEs) have flourished for more than a decade. However, it is still challenging to further enhance their biocatalytic performances due to the limited strategies ...to tune the electronic structures of active centers. Here, a new path is reported for the de novo design of the d electrons of active centers by modulating the electron transfer in vanadium‐based AEs (VOx‐AE) via a unique Zn–O–V bridge for efficient reactive oxygen species (ROS)‐catalysis. Benefiting from the electron transfer from Zn to V, the V site in VOx‐AE exhibits a lower valence state than that in V2O5, which results in charge‐filled V‐dyz orbital near the Fermi level to interfere with the formation of sigma bonds between the V‐dz2 and O‐pz orbitals in H2O2. The VOx‐AE exhibits a twofold Vmax and threefold turnover number than V2O5 when catalyzing H2O2. Meanwhile, the VOx‐AE shows enhanced catalytic eradication of drug‐resistant bacteria and achieves comparable wound‐treatment indexes to vancomycin. This modulating charge‐filling of d electrons provides a new direction for the de novo design of nanomaterials‐based AEs and deepens the understanding of ROS‐catalysis.
A new vanadium‐based artificial enzyme (VOx‐AE) for efficient reactive oxygen species (ROS)‐catalysis is synthesized by modulating the d electrons in the active centers via a unique Zn–O–V bridge structure. Experimental and theoretical results demonstrate that the VOx‐AE exhibits optimal adsorption/dissociation of oxygen‐intermediates, thus showing enhanced ROS catalytic activity and augmented eradication of drug‐resistant bacteria and comparable wound‐treatment indexes to antibiotics.
•The advances on engineering MOFs for the water electrolysis are concluded.•The modulation of coordination structures and metal environments is highlighted.•The mechanism of HER and OER in water ...electrolysis is introduced.•Applications of MOF-engineered electrocatalysts are discussed.
Water electrolysis has been playing an increasingly vital role in the production of renewable hydrogen energy and representing a powerful way to relieve the dependence on fossil fuels effectively. Developing electrocatalysts with high activity, stability, and low cost to reduce the overpotential and improve electrocatalytic efficiency is a pressing task currently. MOF materials have stood out among various electrocatalysts for their tunable coordination structures and metal atom environments that impose essential influence on the practical catalytic performance. Here, we have concluded and discussed the most pivotal advances in engineering MOF nanoarchitectures for efficient water electrolysis thoroughly. First, we give a comprehensive overview for the modulation of coordination structures and metal atom environments in MOF and MOF-derived catalysts. Subsequently, their applications in water splitting are discussed according to the coordination structure and the local atomic environment. We hope this timely review will provide critical information and insights for the further exploration of MOF-based/-derived electrocatalysts for water electrolysis.
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