Postsynthetic Modification of NU-1000 for Designing a Polyoxometalate-Containing Nanocomposite with Enhanced Third-Order Nonlinear Optical Performance

Abstract

For the advancement of laser technologies and optical engineering, various types of new inorganic and organic materials are emerging. Metal−organic frameworks (MOFs) reveal a promising use in nonlinear optics, given the presence of organic linkers, metal cluster nodes, and possible delocalization of π-electron systems. These properties can be further enhanced by the inclusion of solely inorganic materials such as polyoxometalates as prospective low-cost electron-acceptor species. In this study, a novel hybrid nanocomposite, namely, SiW 12 @NU-1000 composed of SiW 12 (H 4 SiW 12 O 40 ) and Zrbased MOF (NU-1000), was assembled, completely characterized, and thoroughly investigated in terms of its nonlinear optical (NLO) performance. The third-order NLO behavior of the developed system was assessed by Z-scan measurements using a 532 nm laser. The effect of two-photon absorption and self-focusing was significant in both NU-1000 and SiW 12 @NU-1000. Experimental studies suggested a much superior NLO performance of SiW 12 @NU-1000 if compared to that of NU-1000, which can be assigned to the charge-energy transfer between SiW 12 and NU-1000. Negligible light scattering, good stability, and facile postsynthetic fabrication method can promote the applicability of the SiW 12 @NU-1000 nanocomposite for various optoelectronic purposes. This research may thus open new horizons to improve and enhance the NLO performance of MOF-based materials through π-electron delocalization and compositing metal−organic networks with inorganic molecules as electron acceptors, paving the way for the generation of novel types of hybrid materials for prospective NLO applications.

Pillared-MOF@NiV-LDH Composite as a Remarkable Electrocatalyst for Water Oxidation

“…Metal–organic frameworks (MOFs) represent a prominent class of compounds with a giant diversity of prospective applications in different fields due to their intrinsic features such as large surface area, adaptable structure and porosity, and simple synthesis. − MOFs are also of interest for applications in OER, where the open channels present in the structures may permit faster and more efficient access or reagents and the release of gas products during the electrochemical reactions. , Besides, the presence of homogeneously distributed metal centers in porous MOF structures can provide the necessary amount of well-exposed electroactive sites for electrochemical reactions. , To date, various Co-containing electrocatalysts have been used for water splitting and OER, but to the best of our knowledge, any composite between a pillared-MOF and LDH has not been reported as an electrocatalyst.…”

A Dual-Purpose Ce(III)–Organic Framework with Amine Groups and Open Metal Sites: Third-Order Nonlinear Optical Activity and Catalytic CO2 Fixation

“…Comparison of the NLO coefficients led to the results summarized in Table 3, which are generally superior to those of other MOFs. 24 Given the extensive range of the n 2 and β parameters described for various MOFs, a comparison of the results is not straightforward. Besides, picosecond (ps) or femtosecond (fs) pulses are usually used to characterize n 2 and β in MOFs and subsequently prevent thermal effects, though longer pulses or even continuous-wave (CW) stimulations are preferred in real-world applications.…”

Metal‐Organic Frameworks (MOFs) and Their Derivatives for Electrocatalytic Carbon Dioxide (CO2) Reduction to Value‐added Chemicals: Recent Advances and New Challenges

“…The synergistic effect between MOFs and functional components contributes to enhance the electrochemical properties of MOFs composites. [16][17][18] More importantly, some MOFs have CO 2 adsorption capacity, which is beneficial to increase the local CO 2 concentration of MOFs during CO 2 RR. One point to note in particular is that the genuine active site of the MOF should be meticulously judged when pristine MOFs are subjected to electrocatalytic CO 2 RR, as the MOF structure may evolve under working time.…”

“…They can be combined with functional materials, such as carbon, polymers, metal nanoparticles and polyoxometalates (POMs), to build MOFs composites. The synergistic effect between MOFs and functional components contributes to enhance the electrochemical properties of MOFs composites [16–18] . More importantly, some MOFs have CO 2 adsorption capacity, which is beneficial to increase the local CO 2 concentration of MOFs during CO 2 RR.…”