Organic Frameworks Research Articles

Construction of COFs@MoS2-Pd Hierarchical Tubular Heterostructures for Enhanced Catalytic Performance.

Here, we report ternary COFs@MoS2-Pd hybrids with an innovative self-sacrificial approach. MoO3@Covalent organic frameworks (COFs) microcables were first prepared and then two-dimensional MoS2 nanosheets (NSs) were integrated onto the surface of COFs, as COFs@MoS2, after treatment with hydrothermal reaction. The MoS2 NSs were used as an excellent support to introduce Pd nanoparticles (NPs) thanks to their reducing ability for the formation of the ternary COFs@MoS2-Pd hybrids. While COF microtubes improved the electrical conductivity of the hybrid materials, they also decreased the aggregation of MoS2 NSs, as a contribution to the enhanced catalytic performance. The mild reaction between MoS2 and Pd2+ ions realized the dense distribution of Pd NPs onto COFs@MoS2 for abundant active sites to further improve the catalytic performance. Thus, the hierarchical MoS2-based ternary hybrids were prepared with the enhanced catalytical performance as validated with the enzyme-like catalysis and the reduction of 4-nitrophenol.

Mechanism for airborne ozone decomposition on X-MIL-53(Fe) (X = H, NH2, NO2)

Ground−level ozone (O3) pollution poses a significant threat to both ecosystem sustainability and human health. The catalytic decomposition of O3 presents as a promising technology to address the issues of O3 pollution. This study undertook the synthesis of various functionalized metal−organic framework (MOF) catalysts (i.e., X-MIL-53(Fe) (X = H, NH2, NO3)) to delve into the influence of ligand functional groups on skeletal structure and catalytic efficacy, particularly focusing on unraveling the mechanism of O3 catalytic decomposition under humid conditions. NH2-MIL-53(Fe) catalyst achieved complete O3 decomposition under ambient temperature and high humidity conditions (RH=75 %), exhibiting a reaction rates (mol·m−2·s−1) 129 and 10.5 times greater than that of MIL-53(Fe) and NO2-MIL-53(Fe). The NH2 group promotes electron flow within the backbone towards the hydroxyl group (OH) linked to Fe atom. In humid O3, H2O molecules augment the interaction between O3 and NH2-MIL-53(Fe), and OH is converted to·O2− after deprotonation, promoting O3 decomposition. Additionally, leveraging three−dimensional (3D) printing technology, a monolithic catalyst for O3 decomposition was prepared for application. This study not only advances understanding of the mechanisms underlying O3 decomposition but also offers practical solutions for addressing O3 pollution at humid conditions.

Aqueous Afterglow Dispersion Enabling On‐Site Ratiometric Sensing of Mercury Ions

AbstractPollution caused by heavy metal ions has become a global issue owing to their severe threat to the ecological environment and human health. However, it remains a considerable challenge to detect heavy metal ions in an efficient, selective, and high signal‐to‐noise ratio way. Herein, a portable and sensitive method is presented to probe Hg2+ by using an ultralong afterglow dispersion. The in situ encapsulation of phosphorescent carbon dots (CDs) within rigid hydrogen‐bonded organic frameworks (HOFs) leads to ultralong room temperature phosphorescence (RTP) in water with a maximum lifetime of up to 974.86 ms. Moreover, the resultant CDs@HOFs material exhibits robust and long‐term RTP emission with enhanced performance under strongly acidic or alkaline conditions, which contributes to the practical detection of Hg2+ in water. As such, an efficient and sensitive afterglow probe is facilely fabricated by integrating CDs@HOFs with a Hg2+ probe Rhodamine B derivative (RhBTh), demonstrating selective sensing of Hg2+ with greatly improved signal‐to‐noise ratios based on the triplet‐singlet Förster resonance energy transfer system (TS‐FRET). This work not only provides a reliable and versatile method for realizing robust RTP emission in water, but also expands the applications of afterglow materials in the field of optical sensing of toxic analytes.

Inside Back Cover

Metal−organic frameworks (MOFs) offer a versatile platform to investigate emergent physics, the collective behavior of condensed matter stemming from many‐body interactions, thanks to their atomic‐level designability and high spatial ordering. Strong correlations, superconductivity, charge density wave, long‐range magnetic order, and quantum spin liquid phenomena in MOFs have been evidenced recently. These pioneering studies demonstrate the great potential of MOFs as quantum materials yet reveal challenges for their deep physical characterizations. More details are discussed in the Emerging Topic by Wang et al. on page 2514—2519.image

A smartphone-assisted electrochemiluminescent biosensor for highly sensitive detection of miRNA-21 based on Ru(bpy)2(L)4+@MOF-5.

A smartphone-assisted electrochemiluminescence (ECL) strategy based on Ru(bpy)2(L)4+ as chromophores confined with metal - organic frameworks (Ru(bpy)2(L)4+@MOF-5) for the signal-amplified detection of miRNA-21 was developed. We synthesized a derivative of tris(2,2'-bipyridyl)ruthenium(II) complex (Ru(bpy)2(L)4+) with high charges, which can be loaded into the MOF-5 by strong electrostatic interaction to prevent from leakage. In addition, nucleic acid cycle amplification was used to quench the signal of Ru(bpy)2(L)4+@MOF-5 by ferrocene. This method was applied to detect the concentration of miRNA-21 ranging from 1.0 × 10-14-1.0 × 10-9 M with a low LOD of 7.2 fM. This work demonstrated the construction of a signal quenching strategy ECL biosensor for miRNA using Ru(bpy)2(L)4+@MOF-5 systems and its application in smartphone-assisted ECL detection.

Integration of Open Metal Sites in an Amino-Functionalized Sm(III)-Organic Framework toward Enhanced Third-Order Nonlinear Optical Property.

A variety of new inorganic and organic materials have emerged to advance laser technologies and optical engineering. A rational design approach can contribute significantly to fabricating nonlinear optically active metal-organic frameworks (MOFs) by considering the underlying structure-property linkage. Here, it has been embarked on a study of novel samarium(III) MOF, ([Sm2(ata)3(DMF)4]·DMF (ata2-: 2-aminoterephthalate), abbreviated as NH2-Sm-MUM-4) with enhanced nonlinear optical (NLO) properties. The crystal structure of this MOF represents a 6-connected framework with a pcu topology and distinctive characteristics, including open metal sites, free amine groups, and great stability, making it suitable for third-order NLO activity. The nonlinear index of refraction (n2) revealed the self-focusing impacts of NH2-Sm-MUM-4 at different incident intensities. The highest value of n2 and β related to 10 mw power of incident intensity are 5.15 cm2/W and 2.65 cm/W, respectively. As far as the authors know, this is the first study examining the potential systematic structural-property associations in Sm-MOFs considering improved third-order NLO properties.

Zr‐MOF Nanosheets Featuring Benzothiadiazoles Enable Efficient Visible Light Driven Photooxidation of Sulfides and Amines

AbstractUltrathin zirconium‐based metal−organic framework (MOF) nanosheets, embedded with photochromic units, are expected to be highly efficient heterogeneous photocatalysts, thanks to their rich catalytic sites, short diffusion paths, and effective separation of photogenerated charge carriers. Herein, we reported the synthesis of novel Zr‐MOF nanosheets (Zr‐BTDB) through a solvothermal synthesis that integrates benzothiadiazole (BTz) as a photochromic moiety within the framework of MOF. The Zr‐BTDB nanosheets processes a [Zr12(μ3‐O)8(μ3‐OH)8(μ2‐OH)6] cluster with hcp topology. Importantly, Zr‐BTDB nanosheets exhibit excellent photocatalytic activity for the photooxidation of sulfides and amines at room temperature under blue light irradiation. Notably, these nanosheets maintain their photocatalytic activity and selectivity for up to five cycles without significant loss of activity and crystallinity. Systematical catalytic reactions revealed that the Zr‐BTDB nanosheets enable the generation of singlet oxygen (1O2) and superoxide radical (O2⋅−) under visible light irradiation, which is critical reactive oxygen species for the photooxidation of sulfides and benzylamines. Our work represents a straightforward route for the preparation of ultrathin, water stable, and visible‐light‐activated Zr‐MOF nanosheets, offering new potentials for the selective photooxidation of sulfides and amines in an eco‐friendly way.

Dual‐Mode Bionic Visual–Olfactory Co‐Sensory for On‐Site Biogenic Amines Recognition and Food Freshness Prediction

AbstractThe thriving of high‐performance artificial synaptic neuromorphic platforms poses a significant challenge for creating bionic sensors that can integrate multi‐sensory information. For the purpose of realizing this objective, promising bionic visual‐olfactory co‐sensory artificial synaptic devices are developed based on a hydrogen‐bonded organic framework (Eu@HOF‐12). This probe is capable of dual‐emissive‐responsive to biogenic amines (BAs), which are essential indicators for the evaluation of food freshness. Importantly, it demonstrates outstanding advantages, including high sensitivity, ultrafast responses (<6 s), and practicability of recyclability, which can be combined with smartphones for on‐site BAs detection via the colorimetric and ratiometric hydrogel sensor. Besides, a bionic visual‐olfactory co‐sensory based on the human‐computer interaction platform is constructed, which can realize the identification of five types of BAs with high precision through the specific odor fingerprint. Meanwhile, a logic device is utilized for the rapid identification of food freshness considering the hydrogel sensor's dual‐mode responses to BAs. Overall, this research develops an odor visualization strategy that enables on‐site, real‐time, and sensitive monitoring of food quality assessment. In addition, a quantitative assessment system is designed for fast, damage‐free, and accurate assessment of food freshness, ultimately reducing food waste and generating significant economic value.

γ-Cyclodextrin-metal organic framework as a carrier for trans-N-p-coumaroyltyramine: A study of drug solubability, stability, and inhibitory activity against α-glucosidase.

γ-Cyclodextrin-based metal-organic frameworks (γ-CD-MOF) were successfully synthesized using the solvent diffusion method and applied as carriers for trans-N-p-coumaroyltyramine (N-p-t-CT, NCT) to study the solubability, stability, sustained release and inhibitory activity against α-glucosidase. The solubilization effect of γ-CD-MOF on N-p-t-CT was performed using impregnation (NCT@CD-MOF-1) and co-crystallization (NCT@CD-MOF-2) methods. X-ray diffraction, scanning electron microscope (SEM), fourier transform infrared spectrometer (FTIR), and N2 adsorption/desorption were used to characterize the MOFs before and after loading NCT. The results showed that NCT@CD-MOF-2 had a better solubability for N-p-t-CT, 145.03μg/mg of drug loading capacity could be achieved, and the solubility of NCT@CD-MOF-2 in water was 366 times higher than free N-p-t-CT. In addition, the stabilities of N-p-t-CT under temperature, UV light and pH conditions were greatly improved after encapsulation in γ-CD-MOF. Furthermore, NCT@CD-MOFs had a sustained release of N-p-t-CT over an extended period in vitro due to the primary encapsulation in pore structures. Notably, γ-CD-MOF loaded with N-p-t-CT showed superior inhibitory activity against α-glucosidase compared to free N-p-t-CT. Cytotoxicity studies demonstrated that NCT@CD-MOF-2 had low toxicity in vitro and perfect biocompatibility with HL-7702 cells, and γ-CD-MOF could reduce the toxicity of free N-p-t-CT at higher concentrations.

In Situ Synthesized HOF Ion Rectification Membrane with Ultrahigh Permselectivity for Nanofluidic Osmotic Energy Harvesting

AbstractThe utilization of salt concentration gradients as a renewable energy source represents a pivotal solution to the energy crisis. However, it is a persistent challenge to fabricate high‐performance ion permeable membranes with excellent ion permselectivity. In this work, hydrogen‐bonded organic framework (HOF) is in situ growth on anodic aluminum oxide (AAO) via chemical‐binding and solution‐processing strategy. The hydrogen bonding and π–π interactions forming the porous structure and the internal unprotonated carboxyl groups endow the HOF with superior cation selectivity and ion permeability. Furthermore, benefiting from the remarkable asymmetry of the prepared nanofluidic membrane arising from structure and charge of AAO and HOF, the HOF/AAO presents outstanding ion current rectification (ICR) characteristic, which can eliminate the ion concentration polarization (ICP) and power loss. Therefore, an impressive output power density with 500‐fold NaCl gradient is achieved as 75.2 W m−2 using the as‐prepared HOF/AAO, which is superior to most of reported membranes (7.0–40.0 W m−2). To show the critical role of HOF, 2D and 3D MOF with the same monomers are also synthesized, achieving decreased power densities of 36.2 and 58.3 W m−2 respectively. The present work provides a novel strategy to develop high‐performance nanofluidic ICR membranes for osmotic energy harvesting.

Effective Enrichment of Free Radicals through Nanoconfinement Boosts Electrochemiluminescence of Carbon Dots Derived from Luminol.

Local enrichment of free radicals at the electrode interface may open new opportunities for the development of electrochemiluminescence (ECL) applications. The sensing platform was constructed by assembling ECL-emitting luminol derived carbon dots (Lu CDs) onto the heterojunction Tungsten disulfide/Covalent organic frameworks (WS2@COF) for the first time, establishing a nanoconfinement-reactor with significantly heightened ECL intensity and stability compared to the Lu CDs-H2O2 system. This enhanced performance is credited to the COF domain's restricted pore environment, where WS2@COF exhibits a more negative adsorption energy for H2O2, effectively enriching H2O2 in the catalytic edge sites of WS2. Furthermore, the internal electric field at the WS2 and COF interface accelerates electron flow, boosting WS2's catalytic activity and achieving domain-limited catalytic enhancement of ECL. Self-designed DNA nanomachines combined with cascading molecular keypad locking mechanisms are integrated into the biosensors, effectively guaranteeing the accuracy of the sensing process while providing crucial safeguards for molecular diagnostics and information security applications. In essence, this innovative approach represents the first system to enhance local free radical concentrations by enriching co-reactants on the electrode surface through nanoconfinement catalysis, yielding heightened ECL luminescence intensity. The potential impact of this novel strategy and sensing mechanism on real-bioanalysis applications is promising.

Effective Enrichment of Free Radicals through Nanoconfinement Boosts Electrochemiluminescence of Carbon Dots Derived from Luminol

Local enrichment of free radicals at the electrode interface may open new opportunities for the development of electrochemiluminescence (ECL) applications. The sensing platform was constructed by assembling ECL‐emitting luminol derived carbon dots (Lu CDs) onto the heterojunction Tungsten disulfide/Covalent organic frameworks (WS2@COF) for the first time, establishing a nanoconfinement‐reactor with significantly heightened ECL intensity and stability compared to the Lu CDs‐H2O2 system. This enhanced performance is credited to the COF domain's restricted pore environment, where WS2@COF exhibits a more negative adsorption energy for H2O2, effectively enriching H2O2 in the catalytic edge sites of WS2. Furthermore, the internal electric field at the WS2 and COF interface accelerates electron flow, boosting WS2's catalytic activity and achieving domain‐limited catalytic enhancement of ECL. Self‐designed DNA nanomachines combined with cascading molecular keypad locking mechanisms are integrated into the biosensors, effectively guaranteeing the accuracy of the sensing process while providing crucial safeguards for molecular diagnostics and information security applications. In essence, this innovative approach represents the first system to enhance local free radical concentrations by enriching co‐reactants on the electrode surface through nanoconfinement catalysis, yielding heightened ECL luminescence intensity. The potential impact of this novel strategy and sensing mechanism on real‐bioanalysis applications is promising.

Preparation of high temperature proton exchange membranes with multilayered structures through alternate deposition of carbon dots@Metal organic framework and Sulfonated Poly(Ether Ketone)

High temperature proton exchange membranes (HTPEMs) with multilayered structures based on carbon dots@metal organic framework (CDs@MOF) and Sulfonated Poly(Ether Ketone) (SPEEK) have been prepared with the spin coating technique. In this research, carbon dots (CDs) are self-assembled with metal organic framework (MOF) to form the composite of CDs@MOF. Successive proton conduction channels consisting of CDs@MOF and sulfonated groups in SPEEK facilitate to conduct protons in multilayered structures of the prepared composite membranes. Additionally, CDs@MOF can combine phosphoric acid (PA) molecules deriving from the formed intermolecular hydrogen bonding. The proton conductivity is further improved because of the multilayered structures reducing the proton conduction resistance. Specifically, the (SPEEK/40%CDs@MOF)3/PA membrane exhibits the maximum proton conductivity of (5.02 ± 0.64) × 10−2 S/cm at 160 °C. Notably, the proton conductivity can retain 1.53 × 10−2 S/cm at 80 °C after a 200 h non-stop test. The open circuit voltage peak and power density of a single fuel cell based on the (SPEEK/40%CDs@MOF)3/PA membrane respectively reach 0.95 V, 258.2 mW/cm2 at 100 °C and 0.96 V, 369.9 mW/cm2 at 120 °C.

Hydrogen‐Bonded Organic Frameworks‐based Electrolytes with Controllable Hydrogen Bonding Networks for Solid‐State Lithium Batteries

AbstractThe lack of stable solid‐state electrolytes (SSEs) with high‐ionic conductivity and the rational design of electrode/electrolyte interfaces remains challenging for solid‐state lithium batteries. Here, for the first time, a high‐performance solid‐state lithium‐oxygen (Li−O2) battery is developed based on the Li‐ion‐conducted hydrogen‐bonded organic framework (LHOF) electrolyte and the HOF‐DAT@CNT composite cathode. Benefiting from the abundant dynamic hydrogen bonding network in the backbone of LHOF‐DAT SSEs, fast Li+ ion transport (2.2×10−4 S cm−1), a high Li+ transference number (0.88), and a wide electrochemical window of 5.05 V are achieved. Symmetric batteries constructed with LHOF‐DAT SSEs exhibit a stably cycled duration of over 1400 h with uniform deposition, which mainly stems from the jumping sites that promote a uniformly high rate of Li+ flux and the hydrogen‐bonding network structure that can relieve the structural changes during Li+ transport. LHOF‐DAT SSEs‐based Li−O2 batteries exhibit high specific capacity (10335 mAh g−1), and stable cycling life up to 150 cycles. Moreover, the solid‐state lithium metal battery with LHOF‐DAT SSEs endow good rate capability (129.6 mAh g−1 at 0.5 C), long‐term discharge/charge stability (210 cycles). The design of LHOF‐DAT SSEs opens an avenue for the development of novel SSEs‐based solid‐state lithium batteries.

Vinylene‐linked Donor‐π‐Acceptor Metal‐Covalent Organic Framework for Enhanced Photocatalytic CO2 Reduction

Intramolecular charge separation driving force and linkage chemistry between building blocks are critical factors for enhancing the photocatalytic performance of metal‐covalent organic frameworks (MCOF) based photocatalyst. However, robust achieving both simultaneously has yet to be challenging despite ongoing efforts. Here we develop a fully π‐conjugated vinylene‐linked multivariate donor‐π‐acceptor MCOF (D‐π‐A, termed UJN‐1)by integrating integrating benzyl cyanides linker with multiple functional building blocks of electron‐rich triphenylamine and electron‐deficient copper‐cyclic trinuclear units (Cu‐CTUs) moieties, featuring with strong intramolecular charge separation driving force, extended conjugation degree of skeleton, and abundant active sites. The incorporation of Cu‐CTUs acceptor with electron‐withdrawing ability and concomitantly giant charge separation driving force can efficiently accelerate the photogenerated electrons transfer from triphenylamine to Cu‐CTUs, revealing by experiments and theoretical calculations. Benefiting from the synergistically effect of D‐π‐A configuration and vinylene linkage, the highly‐efficient charge spatial separation is achieved. Consequently, UJN‐1 exhibits an excellent CO formation rate of 114.8 μmol g‐1 in 4 h without any co‐catalysts or sacrificial reagents under visible light, outperforming those analogous MCOFs with imine‐linked (UJN‐2, 28.9 μmol g‐1) and vinylene‐linked COF without Cu‐CTU active sites (UJN‐3, 50.0 μmol g‐1), emphasizing the role of charge separation driving force and linkage chemistry in designing novel COFs‐based photocatalyst.

Modulation of animal and plant tissue growth with collagen‐starch‐organic molybdenum networks hydrogel biomatrices

AbstractThe development of hydrogel biomatrices with potential to modulate animal and plant tissue growth is ongoing. In this study, molybdenum bio‐metal–organic frameworks (MOFs) (Mo‐bioMOFs) incorporating essential amino acids such as l‐histidine (Mo‐His), l‐phenylalanine (Mo‐Phe), and l‐tryptophan (Mo‐Trp) were encapsulated in semi‐interpenetrating polymer network (semi‐IPN) hydrogels composed of collagen and starch. The structure and properties of these materials show dependence on the amino acid that constitutes the Mo‐bioMOFs. The biomatrices have a semi‐crystalline surface with increased porosity when using Mo‐His; this system also benefits swelling. Increased crosslinking, acceleration in gelation, and mechanical improvement are observed for the system based on Mo‐Phe. Methylene blue release experiments were conducted, demonstrating that matrices including Mo‐bioMOFs exhibit controlled release profiles, indicating highly stable retention of Mo‐bioMOFs in the semi‐IPN matrix. The biomatrices enhance the metabolism and proliferation of fibroblasts and monocytes, with Mo‐Trp reducing the secretion of inflammatory cytokines like TNF‐α. The biomatrices exhibit gradual and slow mass loss when exposed to collagenase and commercial vegetable substrates. Both leaf and root cells of tomato plants (Solanum lycopersicum) show increased metabolism and growth when exposed to Mo‐Phe and Mo‐His. Notably, the biomatrix containing Mo‐Phe promotes the most substantial plant growth and foliage after 30 days. These biomatrices have potential applications in chronic wound healing and agriculture.

Atmospheric modulation of apparent electrical conductivity in a metal−organic framework

Combining high surface area and efficient charge transport, electrically conductive metal−organic frameworks (MOFs) find wide applications in energy storage, sensing, and electrocatalysis. Reliable characterization of electrical conductivity, the key metric for assessing this class of materials, remains challenging due to its high sensitivity to the atmosphere. Herein, through electrical characterization of an exemplary MOF, Cd2(TTFTB) (TTFTB4− = tetrathiafulvalene tetrabenzoate), under various controlled atmospheres, we show that adsorption of water in humid air or N2 improves the apparent room-temperature electrical conductivity by one to two orders of magnitude compared to the values observed in dry atmospheres. This observation in conjunction with spectroscopic characterization, structural analysis, and band structure calculations indicates significant contribution of water-mediated proton conductivity and/or proton-electron coupling to the apparent electrical conductivity. Thus, controlling and reporting atmospheres in electrical conductivity measurements of MOFs is critical to improve their reproducibility and to gain insights into electrical conduction mechanisms.

A Simple and Sequential Strategy for the Introduction of Complexity and Hierarchy in Hydrogen‐Bonded Organic Framework (HOF) Crystals for Environmental Applications

AbstractHydrogen‐bonded organic frameworks (HOFs) are a new class of crystalline porous organic molecular materials (POMMs) with great potential for a diverse range of applications. HOFs face common challenges to POMMs, and in general to purely organic crystals, that is, the difficulty of integrating complexity in crystals. Herein, we propose a simple and sequential strategy for the formation of HOFs with hierarchical superstructures. The strategy is based on controlling the assembly conditions, avoiding the use of any surface functionalization or template, which allows to obtain hierarchical crystalline porous superstructures in an easy manner. As proof of concept, we obtained the first example of core–shell (HOF‐on‐HOF) crystals and HOFs with hierarchical superstructures having superhydrophobicity and trapping abilities for the capture of persistent water contaminants such as oils and microplastics. We expect that this strategy could serve as inspiration for the construction of more intricate multiscale structures that could greatly expand the library of HOF materials.

Toward Multi‐Functionalized Organogermaniums: Diastereoselective Transformations of Germacycles Derived from Cheletropic Reactions of Boron‐Substituted Butadienes with Ge(II) Salts

The field of organogermanium in chemistry has recently attracted attention. Thanks to the inherent features of germanium (Ge), introducing Ge‐based substituents into organic frameworks has enhanced bioactivity and optoelectronic properties of molecules. Herein, the synthesis of multi‐functionalized organogermaniums using Ge(II) salts is reported. The germacycles having an allylboron moiety, which is derived from the (4+1) cycloadditions of the butadienes bearing a boronic ester moiety with Ge(II) salts, can be applied to further allylboration of aldehydes with perfect diastereoselectivity. The obtained allylated adducts enable access to π‐extended organogermaniums with the retention of the stereocenters.

Biosafe, rapid, and ultrahigh‐capacity endotoxin purification in blood by a sustainable and recyclable MOF‐functionalized chitin microsphere adsorbent

AbstractSepsis is responsible for approximately 5.3 million deaths globally each year. Here, we constructed hierarchical chitin microspheres loaded with MOF‐919 (Ch/metal–organic frameworks [MOFs]) for the rapid and efficient removal of lipopolysaccharide (LPS) in complex blood environments. Furthermore, abundant active sites on MOF‐919(Sc) also enable a record‐high adsorption capacity of 9.56 mg/g in biomass‐based adsorbents due to the coordination interactions between endotoxin and MOF‐919(Sc). The LPS level of sepsis rabbits was less than 2 EU/mL (clearance rate >95%) after 90‐min hemoperfusion, showing no adverse effect on the rabbit organs. Additionally, compared to the commonly used LPS scrubber Toraymyxin (polymethyl methacrylate), the chitin adsorbent is significantly more cost‐effective and environmentally friendly. The preparation strategy for hierarchical porous microspheres offers notable advantages in designability, recyclability, and renewability, providing a new approach to sepsis treatment and promising prospects for the biomedical application of sustainable biomass materials.