Mechanochemically-induced glass formation from two-dimensional hybrid organic-inorganic perovskites.

Hybrid organic-inorganic perovskites (HOIPs) occupy a prominent position in the field of materials chemistry due to their attractive optoelectronic properties. While extensive work has been done on the crystalline materials over the past decades, the newly reported glasses formed from HOIPs open up a new avenue for perovskite research with their unique structures and functionalities. Melt-quenching is the predominant route to glass formation; however, the absence of a stable liquid state prior to thermal decomposition precludes this method for most HOIPs. In this work, we describe the first mechanochemically-induced crystal-glass transformation of HOIPs as a rapid, green and efficient approach for producing glasses. The amorphous phase was formed from the crystalline phase within 10 minutes of ball-milling, and exhibited glass transition behaviour as evidenced by thermal analysis techniques. Time-resolved in situ ball-milling with synchrotron powder diffraction was employed to study the microstructural evolution of amorphisation, which showed that the crystallite size reaches a comminution limit before the amorphisation process is complete, indicating that energy may be further accumulated as crystal defects. Total scattering experiments revealed the limited short-range order of amorphous HOIPs, and their optical properties were studied by ultraviolet-visible (UV-vis) spectroscopy and photoluminescence (PL) spectroscopy.

Improving the molecular spin qubit performance in zirconium MOF composites by mechanochemical dilution and fullerene encapsulation.

Enlarging the quantum coherence times and gaining control over quantum effects in real systems are fundamental for developing quantum technologies. Molecular electron spin qubits are particularly promising candidates for realizing quantum information processing due to their modularity and tunability. Still, there is a constant search for tools to increase their quantum coherence times. Here we present how the mechanochemical introduction of active spin qubits in the form of 10% diluted copper(ii)-porphyrins in the diamagnetic PCN-223 and MOF-525 zirconium-MOF polymorph pair can be achieved. Furthermore, the encapsulation of fullerene during the MOF synthesis directs the process exclusively toward the rare PCN-223 framework with a controllable amount of fullerene in the framework channels. In addition to the templating role, the incorporation of fullerene increases the electron spin-lattice and phase-memory relaxation times, T1 and Tm. Besides decreasing the amount of nuclear spin-bearing solvent guests in the non-activated qubit frameworks, the observed improved relaxation times can be rationalized by modulating the phonon density of states upon fullerene encapsulation.

Advancing mechanochemical synthesis by combining milling with different energy sources.

Owing to its efficiency and unique reactivity, mechanochemical processing of bulk solids has developed into a powerful tool for the synthesis and transformation of various classes of materials. Nevertheless, mechanochemistry is primarily based on simple techniques, such as milling in comminution devices. Recently, mechanochemical reactivity has started being combined with other energy sources commonly used in solution-based chemistry. Milling under controlled temperature, light irradiation, sound agitation or electrical impulses in newly developed experimental setups has led to reactions not achievable by conventional mechanochemical processing. This Perspective describes these unique reactivities and the advances in equipment tailored to synthetic mechanochemistry. These techniques - thermo-mechanochemistry, sono-mechanochemistry, electro-mechanochemistry and photo-mechanochemistry - represent a notable advance in modern mechanochemistry and herald a new level of solid-state reactivity: mechanochemistry 2.0.

Low-Dimensional Magnetism in Multivariate Copper/Zinc MOF-74 Materials Formed via Different Mechanochemical Methods.

MOF-74 is an archetypal magnetic metal-organic framework (MOF) family, with metal nodes bridged by 2,5-dioxido-1,4-benzenedicarboxylic acid (H4dobdc) and arranged into one of the simplest representations of the 1D Ising magnetic model. Recently, a novel mechano-synthetic approach opened a pathway toward a series of bimetallic multivariate (1:1) M1M2-MOF-74 materials, with the uniform distribution of metal cations in the oxometallic chains, offering a unique opportunity to investigate low-dimensional magnetism in these heterometallic MOFs. We explore here how different mechanochemical procedures affect the interaction between the metal nodes of the model system of three multivariate copper(II)/zinc(II)-MOF-74 materials, two of which were obtained through a template-controlled procedure, and the third one was obtained by recently developed mechanical MOF-alloying combined with subsequent accelerated aging. While the three Cu/Zn-MOF-74 products have almost identical powder X-ray diffraction (PXRD) diffractograms and Fourier transform infrared spectra, they differ significantly in their magnetic properties, as revealed through detailed magnetization and X-band and multifrequency high-field electron spin resonance measurements. The magnetic results of the three multivariate Cu/Zn-MOF-74s were compared to the properties of the monometallic Cu-MOF-74, which shows antiferromagnetic intrachain and weaker ferromagnetic interchain interactions. Energy-dispersive X-ray spectroscopy/scanning electron microscopy and solid-state nuclear magnetic resonance spectroscopy helped rationalize the observed differences in magnetization, and in situ synchrotron PXRD monitoring of template-controlled MOF formation revealed different reaction pathways when using the zinc or copper intermediates, involving even the fleeting occurrence of a rare MOF-74 polymorph.

Scalable Mechanochemical Amorphization of Bimetallic Cu-Zn MOF-74 Catalyst for Selective CO2 Reduction Reaction to Methanol.

Selective catalytic reduction of CO2 to methanol has tremendous importance in the chemical industry. It mitigates two critical issues in the modern society, the overwhelming climate change and the dependence on fossil fuels. The most used catalysts are currently based on mixed copper and zinc phases, where the high surface of active copper species is a critical factor for the catalyst performance. Motivated by the recent breakthrough in the controllable synthesis of bimetallic MOF-74 materials by ball milling, we targeted to study the potential of ZnCu-MOF-74 for catalytic CO2 reduction. Here, we tested whether the nanosized channels decorated with readily accessible and homogeneously distributed Zn and Cu metal sites would be advantageous for the catalytic CO2 reduction. Unlike the inactive monometallic Cu-MOF-74, ZnCu-MOF-74 shows moderate catalytic activity and selectivity for the methanol synthesis. Interestingly, the postsynthetic mechanochemical treatment of desolvated ZnCu-MOF-74 resulted in amorphization and a significant increase in both the activity and selectivity of the catalyst despite the destruction of the well-ordered and porous MOF-74 architecture. The results emphasize the importance of defects for the MOF catalytic activity and the potential of amorphous MOFs to be considered as heterogeneous catalysts. Scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and 13C magic angle-spinning nuclear magnetic resonance (MAS NMR) were applied to establish quantitative structure-reactivity relationships. The apparent activation energy of rate reaction kinetics has indicated different pathway mechanisms, primarily through reverse water-gas shift (RWGS). Prolonged time on stream productivity, stability and deactivation were assessed, analysing the robustness or degradation of metal-organic framework nanomaterials. Scalable MOF production processes are making the latter more appealing within emerging industrial decarbonisation, in particular for carbon capture and utilisation (CCU) or hydrogen carrier storage. Acknowledging scale, the costs of fabrication are paramount.

Controlling the Polymorphism and Topology Transformation in Porphyrinic Zirconium Metal-Organic Frameworks via Mechanochemistry.

Tetratopic porphyrin-based metal-organic frameworks (MOFs) represent a particularly interesting subclass of zirconium MOFs due to the occurrence of several divergent topologies. Control over the target topology is a demanding task, and reports often show products containing phase contamination. We demonstrate how mechanochemistry can be exploited for controlling the polymorphism in 12-coordinated porphyrinic zirconium MOFs, obtaining pure hexagonal PCN-223 and cubic MOF-525 phases in 20-60 min of milling. The reactions are mainly governed by the milling additives and the zirconium precursor. In situ monitoring by synchrotron powder X-ray diffraction revealed that specific reaction conditions resulted in the formation of MOF-525 as an intermediate, which rapidly converted to PCN-223 upon milling. Electron spin resonance measurements revealed significant differences between the spectra of paramagnetic centers in two polymorphs, showing a potential of polymorphic Zr-MOFs as tunable supports in spintronics applications.

Green and rapid mechanosynthesis of high-porosity NU- and UiO-type metal-organic frameworks.

The use of a dodecanuclear zirconium acetate cluster as a precursor enables the rapid, clean mechanochemical synthesis of high-microporosity metal-organic frameworks NU-901 and UiO-67, with surface areas up to 2250 m2 g-1. Real-time X-ray diffraction monitoring reveals that mechanochemical reactions involving the conventional hexanuclear zirconium methacrylate precursor are hindered by the formation of an inert intermediate, which does not appear when using the dodecanuclear acetate cluster as a reactant.

Polycatenated 2D Hydrogen-Bonded Binary Supramolecular Organic Frameworks (SOFs) with Enhanced Gas Adsorption and Selectivity.

Controlled assembly of two-dimensional (2D) supramolecular organic frameworks (SOFs) has been demonstrated through a binary strategy in which 1,4-bis-(4-(3,5-dicyano-2,6-dipyridyl)pyridyl)naphthalene (2), generated in situ by oxidative dehydrogenation of 1,4-bis-(4-(3,5-dicyano-2,6-dipyridyl)dihydropyridyl)naphthalene (1), is coupled in a 1:1 ratio with terphenyl-3,3',4,4'-tetracarboxylic acid (3; to form SOF-8), 5,5'-(anthracene-9,10-diyl)diisophthalic acid (4; to form SOF-9), or 5,5'-bis-(azanediyl)-oxalyl-diisophthalic acid (5; to form SOF-10). Complementary O-H···N hydrogen bonds assemble 2D 63-hcb (honeycomb) subunits that pack as layers in SOF-8 to give a three-dimensional (3D) supramolecular network with parallel channels hosting guest DMF (DMF = N,N'-dimethylformamide) molecules. SOF-9 and SOF-10 feature supramolecular networks of 2D → 3D inclined polycatenation of similar hcb layers as those in SOF-8. Although SOF-8 suffers framework collapse upon guest removal, the polycatenated frameworks of SOF-9 and SOF-10 exhibit excellent chemical and thermal stability, solvent/moisture durability, and permanent porosity. Moreover, their corresponding desolvated (activated) samples SOF-9a and SOF-10a display enhanced adsorption and selectivity for CO2 over N2 and CH4. The structures of these activated compounds are well described by quantum chemistry calculations, which have allowed us to determine their mechanical properties, as well as identify their soft deformation modes and a large number of low-energy vibration modes. These results not only demonstrate an effective synthetic platform for porous organic molecular materials stabilized solely by primary hydrogen bonds but also suggest a viable means to build robust SOF materials with enhanced gas uptake capacity and selectivity.

Ultrafine Silver Nanoparticles Supported on a Conjugated Microporous Polymer as High-Performance Nanocatalysts for Nitrophenol Reduction.

A conjugated microporous polymer (CMP) material was designed with pore function of cyano and pyridyl groups that act as potential binding sites for Ag+ ion capture. Ultrafine silver nanoparticles (less than 5 nm) were successfully supported on the predesigned CMP material to afford Ag0@CMP composite materials by means of a simple liquid impregnation and light-induced reduction method. Spherical Ag0 nanoparticles with a statistical mean diameter of ca. 3.9 nm were observed and characterized by scanning electron microscopy and transmission electron microscopy. The Ag0@CMP composite materials were consequently exploited as high-performance nanocatalysts for the reduction of nitrophenols, a family of priority pollutants, at various temperatures and ambient pressure. Moreover, the composite nanocatalysts feature convenient recovery and excellent reusability. This work presents an efficient platform to achieve ultrafine metal nanoparticles immobilized on porous supports with predominant catalytic properties by virtue of the structural design and spatial confinement effect available for conjugated microporous polymers.