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This study presents the development and characterization of a smart textile gas sensor based on the integration of ionic liquid (IL)-functionalized Cu3(HHTP)2metal–organic frameworks (MOFs), using electrohydrodynamic jet (e-jet) printing. The sensor was designed for the detection of nitric oxide (NO) gas, a critical target in various environmental and safety applications. Cu3(HHTP)2MOFs were synthesized and subsequently functionalized with 1-Ethyl-3-methylimidazolium trifluoromethanesulfonate (EMIM+Otf–) ionic liquid to enhance their chemiresistive performance toward NO gas. The functionalized MOF was then e-jet printed onto electrospun polylactic acid (PLA) substrates to fabricate smart textile sensors. The IL-functionalized Cu3(HHTP)2sensors demonstrated a 582× increase in conductivity compared to previously reported MOF-based sensors. Additionally, IL functionalization enhanced sensor sensitivity, with a response increasing from less than 5% in pristine MOF@PLA sensors to approximately 570% at 100 ppm of NO gas. Performance was systematically evaluated across NO concentrations ranging from 5 to 300 ppm, achieving a theoretical limit of detection of 3.7 ppm. The sensors exhibited partial reversibility and retained functionality over extended periods and under humid conditions. Comprehensive analyses using SEM, EDX, FTIR, and XRD were performed to assess the crystallinity of MOF deposits and elucidate the sensing mechanism. These findings highlight the potential of e-jet printing of IL-functionalized MOFs for the development of advanced, flexible gas sensors with applications in both civilian and military settings and implications for personal protective wearable technologies.

This paper describes the use of the layered conductive metal–organic framework (MOF) (nickel)3-(hexahydroxytriphenylene)2[Ni3(HHTP)2] as a model system for understanding the process of self-assembly within this class of materials. We confirm and quantify experimentally the role of the oxidant in the synthetic process. Monitoring the deposition of Ni3(HHTP)2with in situinfrared spectroscopy revealed that MOF formation is characterized by an initial induction period, followed by linear growth with respect to time. The presence and identity of oxidizing agents is critical for the coordination-driven self-assembly of these materials and impacts both the length of the induction period and the observed rate of MOF growth. A large excess of hydrogen peroxide results in a 2× increase in the observed deposition rate (9.6 ± 6.8 × 10–4vs 5.0 ± 2.8 × 10–4min–1) over standard reaction conditions, but leads to the formation of large, irregularly shaped particles. Slower deposition rates in the presence of oxygen favor the formation of uniformly sized nanorods (98 ± 38 × 25 ± 6 nm). These quantitative insights into the mechanism of HHTP-based MOF formation provide valuable information about the fundamental aspects of coordination and polymerization that are critical for nanoscale crystal engineering of structure–property relationships in this class of materials.

The relentless growth of metal–organic framework (MOF) chemistry is paralleled by the persistent urge to control the MOFs physical and chemical properties. While this control is mostly achieved by solvothermal syntheses, room temperature procedures stand out as more convenient and sustainable pathways for the production of MOF materials. Herein, a novel approach to control the crystal size and defect numbers of a dihydroxy-functionalized zirconium-based metal–organic framework (UiO-66(OH)2) at room temperature is reported. Through a reaction–diffusion method in a 1D system, zirconium salt was diffused into an agar gel matrix containing the organic linker to form nanocrystals of UiO-66(OH)2with tailored structural features that include crystal size distribution, surface area, and defect number. By variation of the synthesis parameters of the system, hierarchical MOF nanocrystals with an average size ranging from 30 nm up to 270 nm and surface areas between 201 and 500 m2g–1were obtained in a one-pot synthetic route. To stress the importance of crystal size, morphology, and structural defects on the adsorption properties of UiO-66(OH)2, the adsorption capacity of the MOF toward methylene blue dye was tested with the largest and most defected crystals achieving the best performance of 202 mg/g. The distinctive structural characteristics including the hierarchical micromesoporous frameworks, the nanosized particles, and the highly defective crystals obtained by our synthesis procedure are deemed challenging through the conventional synthesis methods. This work paves the way for engineering MOF crystals with tunable physical and chemical properties, using a green synthesis procedure, for their advantageous use in many desirable applications.

Photocatalytic CO2reduction into formate (HCOO–) has been widely studied with semiconductor and molecule-based systems, but it is rarely investigated with covalent organic frameworks (COFs). Herein, we report a novel donor–acceptor COF named Co-PI-COFcomposed of isoindigo and metallated porphyrin subunits that exhibits high catalytic efficiency (∼50 μmol formate g–1h–1) at low-power visible-light irradiation and in the absence of rare metal cocatalysts. Density functional theory calculations and experimental diffuse-reflectance measurements are used to explain the origin of catalytic efficiency and the particularly low band gap (0.56 eV) in this material. The mechanism of photocatalysis is also studied experimentally and is found to involve electron transfer from the sacrificial agent to the excited Co-PI-COF. The observed high-efficiency conversion could be ascribed to the enhanced CO2adsorption on the coordinatively unsaturated cobalt centers, the narrow band gap, and the efficient transfer of the charge originating from the postsynthetic metallation. It is anticipated that this study will pave the way toward the design of new simple and efficient catalysts for photocatalytic CO2reduction into useful products.