Engineering Platelet Membrane-Coated Bimetallic MOFs as Biodegradable Nanozymes for Efficient Antibacterial Therapy.

Nanocatalytic-based wound therapeutics present a promising strategy for generating reactive oxygen species (ROS) to antipathogen to promote wound healing. However, the full clinical potential of these nanocatalysts is limited by their low reactivity, limited targeting ability, and poor biodegradability in the wound microenvironment. Herein, a bio-organic nanozyme is developed by encapsulating a FeZn-based bimetallic organic framework (MOF) (MIL-88B-Fe/Zn) in platelet membranes (PM@MIL-88B-Fe/Zn) for antimicrobial activity during wound healing. The introduction of Zn in MIL-88B-Fe/Zn modulates the electronic structure of Fe thus accelerating the catalytic kinetics of its peroxidase-like activity to catalytically generate powerful ROS. The platelet membrane coating of MOF innovatively enhanced the interaction between nanoparticles and the biological environment, further developing bacterial-targeted therapy with excellent antibacterial activity against both gram-positive and gram-negative bacteria. Furthermore, this nanozyme markedly suppressed the levels of inflammatory cytokines and promoted angiogenesis in vivo to effectively treat skin surface wounds and accelerate wound healing. PM@MIL-88B-Fe/Zn exhibited superior biodegradability, favourable metabolism and non-toxic accumulation, eliminating concerns regarding side effects from long-term exposure. The high catalytic reactivity, excellent targeting features, and biodegradability of these nanoenzymes developed in this study provide useful insights into the design and synthesis of nanocatalysts/nanozymes for practical biomedical applications.

Co Nanoparticles Confined in Mesoporous Mo/N Co-Doped Polyhedral Carbon Frameworks towards High-Efficiency Oxygen Reduction.

Exploiting effective non-noble metal electrocatalysts for oxygen reduction reaction (ORR) is crucial for fuel cells and metal-air batteries. Herein, we designed and fabricated Co nanoparticles confined in Mo/N co-doped polyhedral carbon frameworks (Co-NP/MNCF) derived from polyoxometalate-encapsuled metal-organic framework, which showed comparable ORR performance with commercial Pt/C and a larger diffusion-limited current density. Moreover, the Co-NP/MNCF also exhibited excellent ORR stability and methanol tolerance. These appealing performances can be attributed to the porosity regulation and heteroatom doping of metal-organic framework derived polyhedral carbon frameworks, which could be beneficial for the exposure of more active sites, the optimization of electronic structure and the mass transfer of electrolyte/electron/ion.

Engineering Atomic Sites via Adjacent Dual-Metal Sub-Nanoclusters for Efficient Oxygen Reduction Reaction and Zn-Air Battery.

N-coordinated transition-metal materials are crucial alternatives to design cost-effective, efficient, and highly durable catalysts for electrocatalytic oxygen reduction reaction. Herein, the synthesis of uniformly distributed Cu-Zn clusters on porous N-doped carbon, which are accompanied by Cu/Zn-Nx single sites, is demonstrated. X-ray absorption fine structure tests reveal the co-existence of M-N (M = Cu or Zn) and M-M bonds in the catalyst. The catalyst shows excellent oxygen reduction reaction (ORR) performance in an alkaline medium with a positive half-wave potential of 0.884 V, a superior kinetic current density of 36.42 mA cm-2 at 0.85 V, and a Tafel slope of 45 mV dec-1 , all of which are among the best-reported results. Furthermore, when employed as an air cathode in Zn-Air battery, it reveals a high open-cycle potential of 1.444 V and a peak power density of 164.3 mW cm-2 . Comprehensive experiments and theoretical calculations approved that the high activity of the catalyst can be attributed to the collaboration of the Cu/Zn-N4 sites with CuZn moieties on N-doped carbons.

Cell Membrane and V2C MXene-Based Electrochemical Immunosensor with Enhanced Antifouling Capability for Detection of CD44.

The inactive adsorption and interference of biomolecules in electrochemical biosensors is a topic of intense interest. Directly utilizing native cell membranes to endow electrochemical surfaces with antifouling and biocompatible features is a promising strategy, rather than attempting to synthetically replicate complex biological interface properties. In this study, we present a facial and sensitive sandwich-type antifouling immunoassay through platelet membrane/Au nanoparticle/delaminated V2C nanosheet (PM/AuNPs/d-V2C)-modified electrode as the substrate of sensing interface and methylene blue/aminated metal organic framework (MB@NH2-Fe-MOF-Zn) as an electrochemical signal probe. The biosensor perfectly integrates the high conductivity of AuNPs-loaded V2C MXene with the excellent loading property of NH2-Fe-MOF-Zn to improve the electrochemical sensing performance. In addition, the excellent antifouling properties of the homogeneous cell membrane can effectively prevent the non-specific adsorption of model proteins. The obtained antifouling biosensor possesses the capability of ultrasensitive detection of CD44 and CD44-positive cancer cell in complex liquids and exhibits good analytical performance for the analysis of CD44 with a linear range from 0.5 ng/mL to 500 ng/mL. This strategy of developing cell membrane-based biosensing systems with enhanced antifouling capability can be easily expanded to the construction of other complex biosensors, and the advanced biological probes and analytical methods provide a favorable means to accurately quantify biomarkers associated with tumor progression.

Hollow mesoporous atomically dispersed metal-nitrogen-carbon catalysts with enhanced diffusion for catalysis involving larger molecules.

Single-atom catalysts (SACs) show great promise in various applications due to their maximal atom utilization efficiency. However, the controlled synthesis of SACs with appropriate porous structures remains a challenge that must be overcome to address the diffusion issues in catalysis. Resolving these diffusion issues has become increasingly important because the intrinsic activity of the catalysts is dramatically improved by spatially isolated single-atom sites. Herein, we develop a facile topo-conversion strategy for fabricating hollow mesoporous metal-nitrogen-carbon SACs with enhanced diffusion for catalysis. Several hollow mesoporous metal-nitrogen-carbon SACs, including Co, Ni, Mn and Cu, are successfully fabricated by this strategy. Taking hollow mesoporous cobalt-nitrogen-carbon SACs as a proof-of-concept, diffusion and kinetic experiments demonstrate the enhanced diffusion of hollow mesoporous structures compared to the solid ones, which alleviates the bottleneck of poor mass transport in catalysis, especially involving larger molecules. Impressively, the combination of superior intrinsic activity from Co-N4 sites and the enhanced diffusion from the hollow mesoporous nanoarchitecture significantly improves the catalytic performance of the oxidative coupling of aniline and its derivatives.

Metal-Free Bifunctional Ordered Mesoporous Carbon for Reversible Zn-CO2 Batteries.

The fabrication of Zn-CO2 batteries is a promising technique for CO2 fixation and energy storage. Herein, nitrogen-doped ordered mesoporous carbon (NOMC) is adopted as a bifunctional metal-free electrocatalyst for CO2 reduction and oxygen evolution reaction in the near-neutral electrolyte. The ordered mesoporous structures and abundant N-dopings of NOMC facilitate the accessibility and utilization of the active sites, which endow NOMC with excellent electrocatalysis performance and outstanding stability. Especially, a nearly 100% CO Faradaic efficiency is achieved at an ultralow overpotential of 360 mV for CO2 reduction. When constructed as an aqueous rechargeable Zn-CO2 battery using NOMC as the cathode, it yields a high peak power density of 0.71 mW cm-2 , a good cyclability of 300 cycles, and excellent energy efficiency of 52.8% at 1.0 mA cm-2 .

Multi-shelled hollow layered double hydroxides with enhanced performance for the oxygen evolution reaction.

Hollow materials with a sophisticated structure are promising for various applications with boosted performances and innovative properties. Herein, we report an in situ transformation strategy using multi-layered MOFs as templates to fabricate multi-shelled hollow NiZnCoFe layered double hydroxides (LDHs), which outperformed the double- and single-shelled hollow LDHs and commercial IrO2 in the oxygen evolution reaction.

Bifunctional single-atomic Mn sites for energy-efficient hydrogen production.

The electrocatalytic hydrogen evolution reaction (HER) for H2 production is essential for future renewable and clean energy technology. Screening energy-saving, low-cost, and highly active catalysts efficiently, however, is still a grand challenge due to the sluggish kinetics of the oxygen evolution reaction (OER) in electrolyzing water. Herein, we present a single atomic Mn site anchored on a boron nitrogen co-doped carbon nanotube array (Mn-SA/BNC), which is perfectly combined with the hydrazine electrooxidation reaction (HzOR) boosted water electrolysis concept. The obtained catalyst achieves 51 mV overpotential at the current density of -10 mA cm-2 for the cathodic HER and 132 mV versus the reversible hydrogen electrode for HzOR, respectively. Besides, in a two-electrode overall hydrazine splitting (OHzS) system, the Mn-SA/BNC catalyst only needs a cell voltage of only 0.41 V to output 10 mA cm-1, with strong durability and nearly 100% faradaic efficiency for H2 production. This work highlights a low-cost and high-efficiency energy-saving H2 production pathway.

Regulating the spatial distribution of metal nanoparticles within metal-organic frameworks to enhance catalytic efficiency.

Composites incorporating metal nanoparticles (MNPs) within metal-organic frameworks (MOFs) have broad applications in many fields. However, the controlled spatial distribution of the MNPs within MOFs remains a challenge for addressing key issues in catalysis, for example, the efficiency of catalysts due to the limitation of molecular diffusion within MOF channels. Here we report a facile strategy that enables MNPs to be encapsulated into MOFs with controllable spatial localization by using metal oxide both as support to load MNPs and as a sacrificial template to grow MOFs. This strategy is versatile to a variety of MNPs and MOF crystals. By localizing the encapsulated MNPs closer to the surface of MOFs, the resultant MNPs@MOF composites not only exhibit effective selectivity derived from MOF cavities, but also enhanced catalytic activity due to the spatial regulation of MNPs as close as possible to the MOF surface.