Metal-organic Frameworks Research Articles

Energy Harvester based on Vertical Contact/separation Triboelectric Nanogenerator using the Surface Characteristics of Metal-organic Framework

Energy Harvester based on Vertical Contact/separation Triboelectric Nanogenerator using the Surface Characteristics of Metal-organic Framework

Exploring Supramolecular Frustrated Lewis Pairs.

Frustrated Lewis pairs (FLPs) have rapidly become one of the key metal-free catalysts for a variety of chemical transformations. Embedding these catalysts within a supramolecular assembly can offer improvements to factors such as recyclability and selectivity. In this review we discuss advances in this area, covering key supramolecular assemblies such as metal organic frameworks (MOFs), covalent organic frameworks (COFs), polymers and macrocycles.

Putting Charge Transfer Degree as a Bridge Connecting Surface-Enhanced Raman Spectroscopy and Photocatalysis.

To date, few systematic approach has been established for predicting catalytic performance by analyzing the spectral information of molecules adsorbed on photocatalyst surfaces. Effective charge transfer (CT) between the semiconductor photocatalysts and surface-absorbed molecules is essential for enhancing catalytic activity and optimizing light energy utilization. This study aimed to validate the surface-enhanced Raman spectroscopy (SERS) based on the CT enhancement mechanism in investigating the CT process during semiconductor photocatalytic C-C coupling model reactions. A copper ion doping strategy was employed to simultaneously enhance the SERS effect and catalytic activity of zinc oxide (ZnO) derived from metal-organic framework (MOF). By analyzing molecular fingerprint SERS spectra, we calculated the degree of CT (ρCT), revealing that SERS enhancement is attributed to the CT mechanism. In-situ SERS spectra confirmed a high correlation between the catalytic activity and ρCT of ZnO with varying copper ion doping levels. A range of photoelectric and spectroscopic tests validated the effectiveness of SERS in linking CT to photocatalytic performance, consistent with first-principles density functional theory (DFT) simulations. This finding is also validated in other semiconductor materials and catalytic reactions, demonstrating the broad applicability of ρCT for predicting and evaluating SERS and catalytic activity.

Single-Step Ethylene Purification and MTO Product Separation in a Nitrogen-Rich Microporous Metal-Organic Framework.

The nitrogen-rich metal-organic framework (MOF) NTUniv-75, featuring a melamine (MA) functional group, enables efficient one-step C2H4 purification and methanol-to-olefins (MTO) product separation. At 298 K, its adsorption capacity follows the order C2H2 > C3H6 > C2H6 > C2H4. Breakthrough experiments showed that NTUniv-75 produced pure C2H4 from C2 mixtures with a productivity of 22.5 mL g-1. For MTO products, productivities reached 43.0 mL g-1 (C2H4) and 61.9 mL g-1 (C3H6). Notably, C3H6 addition nearly doubled the C2H4 yield. Modeling revealed that MA aids C2H2/C2H4 separation, while pocket-like apertures favor C2H6 adsorption. Additionally, C-H···π interactions between C2H6 and C3H6 enhance C2H4 yield.

Experimental and Theoretical Study of Two 3D Difunctional Electrocatalytic Hybrid Vanadate-Containing Metal-Organic Motifs.

Two novel 3D inorganic-organic hybrids based on [V6O18]6-/[V3O9]3- clusters, [Cu18(bbpy)18(V6O18)6]·3H2O (1) and [Cu4Ag4(pty)4(V3O9)4]·H2O (2) (bbpy = 3,5-bis(1-benzimidazole) pyridine, pty = 4'-(4″-pyridyl)-2,2':6',2″-terpyridine), were isolated in the same POV/Cu/N-heterocycle ligand reaction systems. Hybrids 1 and 2 possess novel three-dimensional bimetallic frameworks derived from [V6O18]6-/[V3O9]3- clusters and Cu-organic complexes. In 1, bbpy ligands are grafted by Cu2+ to a grid ribbon 2D sheet, which are connected with benzene-like [V6O18]6- to yield a 3D framework. In 2, helical {O-V-O-V-}n chains are bridged by Cu(II) ions into a 2D layer including eight-membered rings {V6Cu2} and six-membered rings {V4Cu2}, and the adjoining sheets are joined by Ag-N coordination bonds to form a framework structure. Moreover, hybrid 1 has superior electrocatalytic properties for nitrite reduction and oxidation of ascorbic acid with electrocatalytic efficiencies of 397.2 and 96%, respectively. Hybrid 2 displays coordinated electrocatalytic performance toward oxidation reaction through V and Cu centers. Meanwhile, the corresponding theoretical studies were conducted to evaluate electrocatalytic active sites and charge distribution.

Exploring the limits of csq-Zr-MOFs in Adsorption Heat Pumps: a computational study of their potential for cooling and heating applications

Adsorption Heat Pumps (AHPs) promise to play a leading role in achieving targets for decarbonization and reducing worldwide energy consumption. Metal-organic frameworks (MOFs) have been extensively explored in recent years as the medium for AHP due to their outstanding tunability, large surface area, and pore volume. In this work, we computationally design a series of Zr-MOFs with a csq topology using organic linkers of varying lengths to investigate the improvement of the coefficient of performance for heating (COPH) and cooling (COPC). Employing DFT methods, we assess the mechanical stability of these csq-Zr-MOFs by analyzing bulk modulus, shear modulus, and Young’s modulus. We set criteria for mechanical stability, requiring hypothetical csq-Zr-MOFs to have superior or at least equal mechanical properties compared to the experimentally obtained reference MOFs: DUT-6, DUT-60, and MOF-399. It is encouraging to observe that mechanically stable, in silico designed csq-Zr-MOF-5T demonstrates superior cooling performance with a COPC = 0.88. Furthermore, 5T approaches the theoretical COPH limit with a COPH = 1.91. This highlights the importance of pore engineering in optimizing MOF properties. In addition to creating new types of MOFs, we advocate for fine-tuning the existing MOFs using molecular simulations as a guidance.

Preparation of a 6FDA-DAM/ODA Mixed Matrix Membrane Doped with MOFs and Its Application in Gas Separation.

Mixed matrix membranes (MMMs) can significantly improve gas separation performance, but the type and state of the filler in the membrane matrix are key indicators for the development of MMMs. Therefore, in this work, 6FDA-DAM/ODA (1:1), metal-organic frameworks (MOFs) with different particle sizes (UiO-66 and UiO-66-NH2) were synthesized, and then MOFs were doped into 6FDA-DAM/ODA to prepare MMMs. The effects of the dopant materials and their particle sizes on the gas separation performance of the membranes were investigated by testing the permeability of the MMMs to H2, CO2, CH4, and N2. When the dopant material was UIO-66, the permeability and selectivity of MMMs for each gas were significantly improved compared with that of the original membrane; when the dopant material was 300 nm UIO-66-NH2 with a loading of 10 wt %, the permeability performance and the CO2/CH4 selectivity increased from 44.1 to 57.2 compared with that of the original membrane. The permeation performance for CO2, N2, and H2 and the selectivity for CO2/N2, H2/N2, and H2/CH4 were also significantly improved. In terms of comprehensive separation performance, doping 300 nm UiO-66-NH2 was better than doping 70 and 400 nm UiO-66-NH2 and also showed excellent performance in 50:50 (vol/vol) CO2/CH4 binary mixed gas separation. This work provides an idea for the fabrication of MMMs for high-performance gas separation.

Intensive and Persistent Chemiluminescence from Orderly Arranged Ligands within Metal-Organic Frameworks for Inflammation Imaging.

Chemiluminescence offers ultrasensitive imaging for the diagnosis of a variety of diseases by removing the interference from excitation light sources. Here, we prepared two chemiluminescent metal-organic frameworks (Mn-ADA and Zn-ADA) by using (2E,2'E)-3,3'-(anthracene-9,10-diyl)diacrylic acid (ADA) as a ligand. In Mn-ADA and Zn-ADA, the Mn atoms and Zn atoms are six-coordinated and eight-coordinated, respectively, and their frameworks are different in spatial structure. Due to the orderly arrangement of the fluorescence ligands and one-dimensional channel control of the diffusion of the reactant, Mn-ADA exhibits superstrong intensity and persistent chemiluminescence compared to ADA. The intensity of Mn-ADA is 43 times higher, and the lifetime is two times longer than that of ADA. Furthermore, different coordination also causes the chemiluminescence intensity of Mn-ADA to be stronger than that of Zn-ADA. It is established that Mn-ADA can detect H2O2 and image inflammation in mice without the excitation light. This methodology demonstrates the potential of metal-organic frameworks (MOFs) to enhance chemiluminescence and offers a new avenue for the development of MOF materials intended for biomedical application.

Fabrication of Dual-Functional MXene@NiCo2S4 Composites with Enhanced Nonlinear Optical and Electrochemical Properties.

The design and synthesis of multifunctional nanomaterials have attracted considerable attention for expanding the range of practical applications. Herein, a metal-organic framework (MOFs)-derived NiCo2S4 attached to MXene is rationally designed and constructed for an optical limiter and supercapacitor. The MOF-derived NiCo2S4 enhances the tendency of hydroxyl groups on the MXene surface to attract metal ions, resulting in the formation of sulfur vacancies. Moreover, MXene offers a high specific surface area to facilitate the rapid complexation of charge carriers. The resultant MXene@NiCo2S4 (MX@NCS) exhibits markedly enhanced nonlinear optical (NLO) and electrochemical properties through synergistic interactions between the components. The NLO properties can be further optimized by adjusting the amount of MX@NCS powder dispersed in methyl methacrylate (MX@NCS)2-6/PMMA) by using the Z-scan technique. Specifically, the (MX@NCS)4/PMMA exhibits the strongest reverse saturable absorption (RSA) and self-defocusing effects at 100 µJ with β = 3.87×102 cm·GW-1 and γ = -5.94×10-4 cm2·GW-1. Concurrently, the constructed supercapacitor shows a superior energy density of 51.21 Wh·kg-1 at a power density of 863.65 W·kg-1. Notably, the present study indicates a novel strategy to explore the application of materials in the development of efficient optical limiter and supercapacitor technologies.

Operando Electro-Oxidation Reconstitution of a Newly Designed 2D Co(II)-MOF on Nickel Foam to Cobalt Oxyhydroxide Nanosheets towards Energy Sustainability: A Holy Grail in Electrocatalytic Water Splitting.

The upsurging of cost-effective de novo electrocatalysts through the operando electro-oxidation approaches holds great promise for the scalable production of green energy in the pursuit of energy sustainability. This work introduces an operando electro-oxidation reconstitution strategy in producing a smart electrocatalyst, cobalt "oxyhydroxide" derived from a newly designed 2D cobalt(II) metal-organic framework (NBU-4) directly grown on nickel foam (NF), NBU-4/NF@CoOOH. The electrocatalyst, NBU-4/NF@CoOOH, exhibits an outstanding overpotential of 76 mV for the hydrogen evolution reaction and 336 mV for the oxygen evolution reaction to achieve a current density of 10 mA/cm2 with remarkable Faradaic efficiencies of 97.1 and 93.4%, respectively, in 1 M aqueous KOH. Unveiling the bifunctionality of NBU-4/NF@CoOOH as the cathode and anode for overall water splitting in 1 M aqueous KOH, a low voltage of 1.65 V was needed to obtain 10 mA/cm2 current density. Nonetheless, NBU-4/NF@CoOOH displayed excellent stability for 12 h as evidenced from the chronopotentiometry recorded at 10 mA/cm2. The outstanding bifunctional electrocatalytic performance and stability of the electrocatalyst for 50 h is attributed to the unique 2D hexagonal nanosheet morphology of NBU-4/NF@CoOOH and the microporous structure with zigzag flow channels of NF, facilitating a faster kinetics through the Co3+ and Ni2+ dual sites synergism.

Photo-enhanced UiO-66/Au Nanoparticles with High Phosphatase-Like Activity for Rapid Degradation and Detection of Paraoxon.

The severe environmental and human health hazards posed by organophosphorus compounds underscore the pressing need for advancements in their degradation and detection. However, practical implementation is impeded by prolonged degradation durations and limited efficiency. Herein, an effective interfacial modification approach is proposed involving the integration of photoactive Au nanoparticles (NPs) onto metal-organic frameworks, resulting in the synthesis of UiO-66/Au NPs exhibiting enhanced hydrolysis activity under light excitation. Under illumination, UiO-66/Au NPs trigger rapid hydrolysis of ethyl-paraoxon within a mere 10-min timeframe, yielding a discernible colorimetric response indicative of extensive hydrolysis. Mechanistic analyses reveal that Au NPs elevate the local catalytic microenvironment temperature of UiO-66/Au NPs under light exposure, facilitating photo-induced charge transfer that enhances the affinity between the Zr6 clusters within UiO-66/Au NPs and the hydrolytic substrate. These cooperative mechanisms significantly boost the hydrolytic efficiency of UiO-66/Au NPs, resulting in a remarkable 17.8-fold enhancement in catalytic performance. Leveraging the superior photo-enhanced hydrolytic capabilities of UiO-66/Au NPs, a colorimetric sensor is developed for the rapid degradation and detection of ethyl-paraoxon, offering a practical and effective solution for addressing the degradation and detection challenges associated with organophosphorus compounds.

Adsorption and Separation by Flexible MOFs.

Flexible metal-organic frameworks(MOFs) offer unique opportunities due to their dynamic structural adaptability. This review explores the impact of flexibility on gas adsorption, highlighting key concepts for gas storage and separation. Specific examples demonstrate the principal effectiveness of flexible frameworks in enhancing gas uptake and working capacity. Additionally, mixed gas adsorption and separation of mixtures are reviewed, showcasing their potential in selective gas separation. The review also discusses the critical role of the single gas isotherms analysis and adsorption conditions in designing separation experiments. Advanced combined characterization techniques are crucial for understanding the behavior of flexible MOFs, including monitoring of phase transitions, framework-guest and guest-guest interactions. Key challenges in the practical application of flexible adsorbents are addressed, such as the kinetics of switching, volume change, and potential crystal damage during phase transitions. Furthermore, the effects of additives and shaping on flexibility and the "slipping off effect" are discussed. Finally, the benefits of phase transitions beyond improved working capacity and selectivity are outlined, with a particular focus on the advantages of intrinsic thermal management. This review highlights the potential and challenges of using flexible MOFs in gas storage and separation technologies, offering insights for future research and application.

Heterogeneous Frustrated Lewis Pair Catalysts: Rational Structure Design and Mechanistic Elucidation Based on Intrinsic Properties of Supports.

ConspectusThe discovery of reversible hydrogenation using metal-free phosphoborate species in 2006 marked the official advent of frustrated Lewis pair (FLP) chemistry. This breakthrough revolutionized homogeneous catalysis approaches and paved the way for innovative catalytic strategies. The unique reactivity of FLPs is attributed to the Lewis base (LB) and Lewis acid (LA) sites either in spatial separation or in equilibrium, which actively react with molecules. Since 2010, heterogeneous FLP catalysts have gained increasing attention for their ability to enhance catalytic performance through tailored surface designs and improved recyclability, making them promising for industrial applications. Over the past 5 years, our group has focused on investigating and strategically modifying various types of solid catalysts with FLPs that are unique from classic solid FLPs. We have explored systematic characterization techniques to unravel the underlying mechanisms between the active sites and reactants. Additionally, we have demonstrated the critical role of catalysts' intrinsic electronic and geometric properties in promoting FLP formation and stimulating synergistic effects. The characterization of FLP catalysts has been greatly enhanced by the use of advanced techniques such as synchrotron X-ray diffraction, neutron powder diffraction, X-ray photoelectron spectroscopy, extended X-ray absorption fine structure, elemental mapping in scanning transmission electron microscopy, electron paramagnetic resonance spectroscopy, diffuse-reflectance infrared Fourier transform spectroscopy, and solid-state nuclear magnetic resonance spectroscopy. These techniques have provided deeper insights into the structural and electronic properties of FLP systems for the future design of catalysts.Understanding electron distribution in the overlapping orbitals of LA and LB pairs is essential for inducing FLPs in operando in heterogeneous catalysts through target electron reallocation by external stimuli. For instance, in silicoaluminophosphate-type zeolites with weak orbital overlap, the adsorption of polar gas molecules leads to heterolytic cleavage of the Alδ+-Oδ- bond, creating unquenched LA-LB pairs. In a Ru-doped metal-organic framework, the Ru-N bond can be polarized through metal-ligand charge transfer under light, forming Ru+-N- pairs. This activation of FLP sites from the framework represents a groundbreaking innovation that expands the catalytic potential of existing materials. For catalysts already employing FLP chemistry to dynamically generate products from substrates, a complete mechanistic interpretation requires a thorough examination of the surface electronic properties and the surrounding environment. The hydrogen spillover ability on the Ru-doped FLP surfaces improves conversion efficiency by suppressing hydrogen poisoning at metal sites. In situ H2-H2O conditions enable the production of organic chemicals with excellent activity and selectivity by creating new bifunctional sites via FLP chemistry. By highlighting the novel FLP systems featuring FLP induction and synergistic effects and the selection of advanced characterization techniques to elucidate reaction mechanisms, we hope that this Account will offer innovative strategies for designing and characterizing FLP chemistry in heterogeneous catalysts to the research community.

NIR-II absorption and photothermal conversion in a photochromic metal-organic framework based on cis-2,2'-biquinoline-4,4'-dicarboxylate.

A BCA cis-coordinated MOF (1) was initially discovered to exhibit electron transfer photochromism. Remarkably, the photogenerated radicals (1P) showed a maximum absorption enhancement peak at 1158 nm, resulting from the synergistic effects of planar π-conjugation induced by cis-coordination and π-π interactions among [BCA]˙˙ radicals, thereby promoting the NIR-II photothermal effect.

Multicolor emission from a 0D-doped hybrid halide (C8H14N2)2CdBr6 single crystal.

Achieving multicolor emission is a fascinating goal that remains challenging for zero-dimensional (0D) hybrid halides. We successfully obtained a three-millimeter-scale 0D (MXDA)2CdBr6 (MXDA = C8H14N22+) single crystal (SC) by the solvothermal method. It serves as an outstanding host for doping with various valence activators, such as Cu+, Mn2+ and Sb3+, and these doped single crystals emit blue (470 nm), yellow (580 nm) and red (618 nm) fluorescence, which accurately cover a large visible region and achieve efficient multicolor emission. (MXDA)2CdBr6:8%Cu+ exhibits a high photoluminescence quantum yield (PLQY) of 60.31% under 320 nm UV excitation, while (MXDA)2CdBr6:10%Mn2+ shows a PLQY of 50.52%. Density functional theory calculations indicate that the hybrid 0D (MXDA)2CdBr6 halide is an indirect bandgap semiconductor with a bandgap value of 3.33 eV. This work expands the new material space for organic-inorganic hybrid halide materials and provides insights for tuning their optical properties.

Ultra-stable and Sensitive X-ray Detectors Using 3D Hybrid Perovskitoid Single Crystals.

Organic-inorganic hybrid perovskites (OIHPs) have shown great potential for direct X-ray detection in security screening and medical diagnostics. However, their humidity stability is compromised due to the susceptibility of the structural components to water molecules, thereby limiting their practical application. In this work, stable and sensitive X-ray detection is achieved using high-quality bulk single crystals of the 3D perovskitoid (DMPZ)Pb2Br6 (DPB, DMPZ = N,N'-dimethyl-pyrazinium), wherein N-acid protons are replaced with hydrophobic alkyl groups. Notably, the crystals maintain phase stability after 60 days of immersion in water at room temperature, demonstrating their significant potential for moisture-stable X-ray detectors. Based on the bulk crystals of DPB, the X-ray detectors are successfully fabricated, achieving a high sensitivity of 6437.2 µC Gyair -1 cm-2 at 70V bias and a detection limit low to 46.7 nGyair s-1, outperforming most low-dimensional perovskite detectors. Most strikingly, the detectors retain 79.6% of their initial sensitivity after 14 days of water immersion, highlighting exceptional moisture stability. This work is the first to construct moisture-stable high-performance X-ray detectors using 3D perovskitoid single crystals, advancing the development of stable X-ray detection.

A point mutation in a wspF-like gene in Pseudoalteromonas lipolytica enhances the anticorrosion activity.

The protection of steel based on microbial biomineralization has emerged as a novel and eco-friendly strategy for corrosion control. However, the molecular basis of the biomineralization process in mineralization bacteria remains largely unexplored. We previously reported that Pseudoalteromonas lipolytica EPS+ strain provides protection against steel corrosion by forming a hybrid biomineralization film. In this study, we identified that a point mutation in the AT00_08765 (wspF-like) gene, responsible for encoding a chemotaxis protein that regulates swimming motility and polysaccharide production, is linked to the observed anticorrosion activity in EPS+ strain. The engineered point mutation mutant strain, designated Δ08765(707A), exhibited similar phenotypes to the EPS+ strain, including colony morphology and cellulose production. Importantly, we demonstrated that moderate swimming motility in Δ08765(707A) plays a pivotal role in the development of a protective mineralization film on the steel surface. Additionally, we found that Δ08765(707A) enhances biofilm formation by rapidly forming small aggregates in the initial stage of biofilm growth. This process facilitated the assembly of more compact and larger mineralization products, effectively inhibiting steel corrosion. In addition, Δ08765(707A) formed a uniform mineralization film that completely covered the steel surface, preventing the formation of sheet-like steel corrosion products. Therefore, this study demonstrates that an engineering strain carrying a point mutation in the AT00_08765 gene can significantly enhance the anticorrosion activity. This enhancement is accomplished through the formation of small bacteria-induced aggregates, followed by the development of larger mineralization products and the creation of a uniform organic-inorganic hybrid film.IMPORTANCEIn this study, we revealed that moderate swimming motility significantly influences the anticorrosion activity of marine Pseudoalteromonas. Furthermore, our study demonstrated that overproduction of cellulose facilitates cell aggregation rapidly during the initial stages of biofilm formation, thereby promoting the development of larger mineralization products and the formation of a uniform organic-inorganic hybrid film on the steel surface. Our findings provide new insights into the biomineralization mechanisms in Pseudoalteromonas lipolytica, potentially catalyzing the advancement of an eco-friendly microbial-driven approach to marine corrosion prevention.

The Design of Intrinsically Conductive Metal‐Organic Frameworks for Thermoelectric Materials

Thermoelectric (TE) materials offer exciting promise in the development of sustainable, green energy alternatives. Ideal TE materials promote high electrical conductivity, whilst effectively scattering phonons for reduced thermal conductivity, thus giving the phonon‐glass electron‐crystal concept. Metal‐organic frameworks (MOFs) have emerged as a versatile class of materials that could meet these criteria. The high crystallinity of MOFs can offer effective pathways for charge transport whilst their intrinsic high porosity yields ultralow thermal conductivity. The high structural diversity of MOFs, owing to the versatile coordination of metal cation/cluster and linker offers the potential to systematically tune their properties for TE performance. This review examines the advancement in the design strategies that have thus far been implemented toward intrinsically conductive MOFs and how these should be tailored for application toward TE materials. By addressing the challenges and leveraging the unique properties of MOFs, future research can pave the way for innovative and efficient TE MOF materials.

Kirkendall Effect-Mediated Transformation of ZIF-67 to NiCo-LDH Nanocages as Oxidase Mimics for Multicolor Point-of-Care Testing of β-Galactosidase Activity and Escherichia coli.

Early and portable detection of pathogenic bacteria is crucial for ensuring food safety, monitoring product quality, and tracing the sources of bacterial infections. Moving beyond traditional plate-culture counting methods, the analysis of active bacterial components offers a rapid means of quantifying bacteria. Here, metal-organic framework (MOF)-derived NiCo-layered double hydroxide nanosheets (LDHs), synthesized via the Kirkendall effect, were employed as highly effective oxidase mimics to generate reactive oxygen species (ROS). These ROS quickly etched gold nanobipyramids (Au NBPs), producing a vivid multicolormetric response. Experimental results and theoretical calculations indicated that the exceptional oxidase-like activity of NiCo-LDHs stemmed from the presence of bimetallic active sites and oxygen vacancies modulating the local electronic structure of LDHs. Additionally, β-galactosidase (β-Gal), a biomarker of Escherichia coli, reacted with p-aminophenyl-β-d-galactopyranoside (PAPG) to form p-aminophenol (PAP), a reducing agent which consumes ROS, thereby inhibiting the etching of Au NBPs. Furthermore, a three-dimensional (3D)-printed point-of-care testing (POCT) shell was designed as a portable device to visually detect β-Gal and E. coli in conjugation with smartphones. This study not only provides a novel approach to the rational design of nanozymes but also establishes a vivid and portably visual biosensing platform for detecting β-Gal activity and pathogenic bacteria.

Semiconducting Cu(I) Framework for Room Temperature NO2 Sensing via Efficient Charge Transfer.

Efficient room-temperature sensors for toxic gases are essential to ensure a safe and healthy life. Conducting frameworks have shown great promise in advancing gas sensing technologies. In this study, two new organic-inorganic frameworks [Cu2X2(PPh3)2(L)]n, CP1 (X = I) and CP2 (X = Br) have been synthesized using (pyridin-4-yl)-N-(4H-1,2,4-triazol-4-yl)methanimine (L) and triphenylphosphine. These frameworks exhibit distinct structural arrangements to generate 1D coordination polymers (CPs). Due to their semiconducting properties, both CPs are fabricated into conventional interdigitated electrodes by drop-casting. Benefitting from the higher electron density of the Cu(I) center, CP1 demonstrates selective sensing for NO2 gas with excellent sensitivity and reversibility. The material offers one of the best room temperature NO2 chemiresistive sensing performances among the MOF/CP-based materials with ultrafast response time (15.5 s @10 ppm). Additionally, convenient synthesis and ease of device fabrication for sensing give the material a distinct advantage. The experimental and theoretical findings collectively suggest that the adsorption of NO2 on the material's surface and the concomitant effective charge transfer between Cu(I) and NO2 are key to its efficacious gas sensing capabilities.