A proxy for oxygen storage capacity from high-throughput screening and automated data analysis.

Oxygen storage and release is a foundational part of many key pathways in heterogeneous catalysis, such as the Mars-van Krevelen mechanism. However, direct measurement of oxygen storage capacity (OSC) is time-consuming and difficult to parallelise. To accelerate the discovery of stable high OSC rare-earth doped ceria-zirconia oxygen storage catalysts, a high-throughput robotic-based co-precipitation synthesis route was coupled with sequentially automated powder X-ray diffraction (PXRD), Raman and thermogravimetric analysis (TGA) characterisation of the resulting materials libraries. Automated extraction of data enabled rapid trend identification and provided a data set for the development of an OSC prediction model, investigating the significance of each extracted quantity towards OSC. The optimal OSC prediction model produced incorporated variables from only fast-to-measure analytical techniques and gave predicted values of OSC that agreed with experimental observations across an independent validation set. Those measured quantities that feature in the model emerge as proxies for OSC performance. The ability to predict the OSC of the materials accelerates the discovery of high-capacity oxygen storage materials and motivates the development of similar high-throughput workflows to identify candidate catalysts for other heterogeneous transformations.

Machine-Learning Prediction of Metal-Organic Framework Guest Accessibility from Linker and Metal Chemistry.

The choice of metal and linker together define the structure and therefore the guest accessibility of a metal-organic framework (MOF), but the large number of possible metal-linker combinations makes the selection of components for synthesis challenging. We predict the guest accessibility of a MOF with 80.5 % certainty based solely on the identity of these two components as chosen by the experimentalist, by decomposing reported experimental three-dimensional MOF structures in the Cambridge Structural Database into metal and linker and then learning the connection between the components' chemistry and the MOF porosity. Pore dimensions of the guest-accessible space are classified into four ranges with three sequential models. Both the dataset and the predictive models are available to download and offer simple guidance in prioritization of the choice of the components for exploratory MOF synthesis for separation and catalysis based on guest accessibility considerations.

High-Throughput Discovery of a Rhombohedral Twelve-Connected Zirconium-Based Metal-Organic Framework with Ordered Terephthalate and Fumarate Linkers.

We report a metal-organic framework where an ordered array of two linkers with differing length and geometry connect [Zr6 (OH)4 O4 ]12+ clusters into a twelve-connected fcu net that is rhombohedrally distorted from cubic symmetry. The ordered binding of equal numbers of terephthalate and fumarate ditopic carboxylate linkers at the trigonal antiprismatic Zr6 core creates close-packed layers of fumarate-connected clusters that are connected along the single remaining threefold axis by terephthalates. This well-defined linker arrangement retains the three-dimensional porosity of the Zr cluster-based UiO family while creating two distinct windows within the channels that define two distinct guest diffusion paths. The ordered material is accessed by a restricted combination of composition and process parameters that were identified by high-throughput synthesis.

Amino Acid Residues Determine the Response of Flexible Metal-Organic Frameworks to Guests.

Flexible metal-organic frameworks (MOFs) undergo structural transformations in response to physical and chemical stimuli. This is hard to control because of feedback between guest uptake and host structure change. We report a family of flexible MOFs based on derivatized amino acid linkers. Their porosity consists of a one-dimensional channel connected to three peripheral pockets. This network structure amplifies small local changes in linker conformation, which are strongly coupled to the guest packing in and the shape of the peripheral pockets, to afford large changes in the global pore geometry that can, for example, segment the pore into four isolated components. The synergy among pore volume, guest packing, and linker conformation that characterizes this family of structures can be determined by the amino acid side chain, because it is repositioned by linker torsion. The resulting control optimizes noncovalent interactions to differentiate the uptake and structure response of host-guest pairs with similar chemistries.

The Anisotropic Responses of a Flexible Metal-Organic Framework Constructed from Asymmetric Flexible Linkers and Heptanuclear Zinc Carboxylate Secondary Building Units.

A new porous and flexible metal-organic framework (MOF) has been synthesized from the flexible asymmetric linker N-(4-carboxyphenyl)succinamate (CSA) and heptanuclear zinc oxo-clusters of formula [Zn7O2(carboxylate)10DMF2] involving two coordinated terminal DMF ligands. The structural response of this MOF to the removal or exchange of its guest molecules has been probed using a combination of experimental and computational approaches. The topology of the material, involving double linker connections in the a and b directions and single linker connections along the c axis, is shown to be key in the material's anisotropic response. The a and b directions remain locked during guest removal, whereas the c axis linker undergoes large changes significantly reducing the material's void space. The changes to the c axis linker involve a combination of a hinge motion on the linker's rigid side and conformational rearrangements on its flexible end, which were probed in detail during this process despite the presence of crystallographic disorder along this axis, which prevented accurate characterization by experimental methods alone. Although inactive during guest removal, the flexible ends of the a and b axis linkers are observed to play a prominent role during DMF to DMSO solvent exchange, facilitating the exchange reaction arising in the cluster.

Chemical control of structure and guest uptake by a conformationally mobile porous material.

Metal-organic frameworks (MOFs) are crystalline synthetic porous materials formed by binding organic linkers to metal nodes: they can be either rigid1,2 or flexible3. Zeolites and rigid MOFs have widespread applications in sorption, separation and catalysis that arise from their ability to control the arrangement and chemistry of guest molecules in their pores via the shape and functionality of their internal surface, defined by their chemistry and structure4,5. Their structures correspond to an energy landscape with a single, albeit highly functional, energy minimum. By contrast, proteins function by navigating between multiple metastable structures using bond rotations of the polypeptide6,7, where each structure lies in one of the minima of a conformational energy landscape and can be selected according to the chemistry of the molecules that interact with the protein. These structural changes are realized through the mechanisms of conformational selection (where a higher-energy minimum characteristic of the protein is stabilized by small-molecule binding) and induced fit (where a small molecule imposes a structure on the protein that is not a minimum in the absence of that molecule)8. Here we show that rotation about covalent bonds in a peptide linker can change a flexible MOF to afford nine distinct crystal structures, revealing a conformational energy landscape that is characterized by multiple structural minima. The uptake of small-molecule guests by the MOF can be chemically triggered by inducing peptide conformational change. This change transforms the material from a minimum on the landscape that is inactive for guest sorption to an active one. Chemical control of the conformation of a flexible organic linker offers a route to modifying the pore geometry and internal surface chemistry and thus the function of open-framework materials.

Encapsulation of Crabtree's Catalyst in Sulfonated MIL-101(Cr): Enhancement of Stability and Selectivity between Competing Reaction Pathways by the MOF Chemical Microenvironment.

Crabtree's catalyst was encapsulated inside the pores of the sulfonated MIL-101(Cr) metal-organic framework (MOF) by cation exchange. This hybrid catalyst is active for the heterogeneous hydrogenation of non-functionalized alkenes either in solution or in the gas phase. Moreover, encapsulation inside a well-defined hydrophilic microenvironment enhances catalyst stability and selectivity to hydrogenation over isomerization for substrates bearing ligating functionalities. Accordingly, the encapsulated catalyst significantly outperforms its homogeneous counterpart in the hydrogenation of olefinic alcohols in terms of overall conversion and selectivity, with the chemical microenvironment of the MOF host favouring one out of two competing reaction pathways.

Stable and ordered amide frameworks synthesised under reversible conditions which facilitate error checking.

ABSTARCT: Covalent organic frameworks (COFs) are network polymers with long-range positional order whose properties can be tuned using the isoreticular chemistry approach. Making COFs from strong bonds is challenging because irreversible rapid formation of the network produces amorphous materials with locked-in disorder. Reversibility in bond formation is essential to generate ordered networks, as it allows the error-checking that permits the network to crystallise, and so candidate network-forming chemistries such as amide that are irreversible under conventional low temperature bond-forming conditions have been underexplored. Here we show that we can prepare two- and three-dimensional covalent amide frameworks (CAFs) by devitrification of amorphous polyamide network polymers using high-temperature and high-pressure reaction conditions. In this way we have accessed reversible amide bond formation that allows crystalline order to develop. This strategy permits the direct synthesis of practically irreversible ordered amide networks that are stable thermally and under both strong acidic and basic hydrolytic conditions.

Encapsulation of an organometallic cationic catalyst by direct exchange into an anionic MOF.

Metal-Organic Frameworks (MOFs) are porous crystalline materials that have emerged as promising hosts for the heterogenization of homogeneous organometallic catalysts, forming hybrid materials which combine the benefits of both classes of catalysts. Herein, we report the encapsulation of the organometallic cationic Lewis acidic catalyst [CpFe(CO)2(L)]+ ([Fp-L]+, Cp = η5-C5H5, L = weakly bound solvent) inside the pores of the anionic [Et4N]3[In3(BTC)4] MOF (H3BTC = benzenetricarboxylic acid) via a direct one-step cation exchange process. To conclusively validate this methodology, initially [Cp2Co]+ was used as an inert spatial probe to (i) test the stability of the selected host; (ii) monitor the stoichiometry of the cation exchange process and (iii) assess pore dimensions, spatial location of the cationic species and guest-accessible space by single crystal X-ray crystallography. Subsequently, the quasi-isosteric [Fp-L]+ was encapsulated inside the pores via partial cation exchange to form [(Fp-L)0.6(Et4N)2.4][In3(BTC)4]. The latter was rigorously characterized and benchmarked as a heterogeneous catalyst in a simple Diels-Alder reaction, thus verifying the integrity and reactivity of the encapsulated molecular catalyst. These results provide a platform for the development of heterogeneous catalysts with chemically and spatially well-defined catalytic sites by direct exchange of cationic catalysts into anionic MOFs.

Acid loaded porphyrin-based metal-organic framework for ammonia uptake.

A porphyrin-based metal-organic framework is shown to be structurally stable towards acid loading using either hydrochloric or formic acid. The capacity of this material as an ammonia sorbent was analysed using micro-breakthrough experiments in both dry and humid ammonia flows. The acid loaded material exhibited excellent uptake in comparison with the parent MOF.

Chemical and structural stability of zirconium-based metal-organic frameworks with large three-dimensional pores by linker engineering.

The synthesis of metal-organic frameworks with large three-dimensional channels that are permanently porous and chemically stable offers new opportunities in areas such as catalysis and separation. Two linkers (L1=4,4',4'',4'''-([1,1'-biphenyl]-3,3',5,5'-tetrayltetrakis(ethyne-2,1-diyl)) tetrabenzoic acid, L2=4,4',4'',4'''-(pyrene-1,3,6,8-tetrayltetrakis(ethyne-2,1-diyl))tetrabenzoic acid) were used that have equivalent connectivity and dimensions but quite distinct torsional flexibility. With these, a solid solution material, [Zr6 O4 (OH)4 (L1)2.6 (L2)0.4 ]⋅(solvent)x , was formed that has three-dimensional crystalline permanent porosity with a surface area of over 4000 m(2) g(-1) that persists after immersion in water. These properties are not accessible for the isostructural phases made from the separate single linkers.

Guest-adaptable and water-stable peptide-based porous materials by imidazolate side chain control.

The peptide-based porous 3D framework, ZnCar, has been synthesized from Zn(2+) and the natural dipeptide carnosine (ß-alanyl-L-histidine). Unlike previous extended peptide networks, the imidazole side chain of the histidine residue is deprotonated to afford Zn-imidazolate chains, with bonding similar to the zeolitic imidazolate framework (ZIF) family of porous materials. ZnCar exhibits permanent microporosity with a surface area of 448 m(2) g(-1) , and its pores are 1D channels with 5 Šopenings and a characteristic chiral shape. This compound is chemically stable in organic solvents and water. Single-crystal X-ray diffraction (XRD) showed that the ZnCar framework adapts to MeOH and H2 O guests because of the torsional flexibility of the main His-ß-Ala chain, while retaining the rigidity conferred by the Zn-imidazolate chains. The conformation adopted by carnosine is driven by the H bonds formed both to other dipeptides and to the guests, permitting the observed structural transformations.

One-pot synthesis of highly crystalline mesoporous TiO2 nanoparticle assemblies with enhanced photocatalytic activity.

We report an unprecedented formation of mesoporous titania via a surfactant-assisted aggregating assembly of TiO(2) nanoparticles. These mesostructures possess a highly crystalline anatase phase, large and accessible pore surface area, and exhibit superior photocatalytic performance.

Compression and aggregation-resistant particles of crumpled soft sheets.

Unlike flat sheets, crumpled paper balls have both high free volume and high compressive strength, and can tightly pack without significantly reducing the area of accessible surface. Such properties would be highly desirable for sheet-like materials such as graphene, since they tend to aggregate in solution and restack in the solid state, making their properties highly dependent on the material processing history. Here we report the synthesis of crumpled graphene balls by capillary compression in rapidly evaporating aerosol droplets. The crumpled particles are stabilized by locally folded, π-π stacked ridges as a result of plastic deformation, and do not unfold or collapse during common processing steps. In addition, they are remarkably aggregation-resistant in either solution or solid state, and remain largely intact and redispersible after chemical treatments, wet processing, annealing, and even pelletizing at high pressure. For example, upon compression at 55 MPa, the regular flat graphene sheets turn into nondispersible chunks with drastically reduced surface area by 84%, while the crumpled graphene particles can still maintain 45% of their original surface area and remain readily dispersible in common solvents. Therefore, crumpled particles could help to standardize graphene-based materials by delivering more stable properties such as high surface area and solution processability regardless of material processing history. This should greatly benefit applications using bulk quantities of graphene, such as in energy storage or conversion devices. As a proof of concept, we demonstrate that microbial fuel electrodes modified by the crumpled particles indeed outperform those modified with their flat counterparts.

Preparation of hydroxyapatite via microemulsion route.

Hydroxyapatite (HAp) was prepared using a microemulsion route in combination with the pH-shock wave method. The samples as received consisted of amorphous aggregated particles, which had remarkable mesoporosity with a narrow pore size distribution. After being heated at 650 degrees C, the A-type carbonate hydroxyapatite was crystallized at 635 degrees C in particles of similar size (40--120 nm) with no internal porosity. At a higher temperature (900 degrees C) a sintering process took place, resulting in network of a larger particles, consisting of HAp and beta-tricalcium phosphate (beta-TCP). The crystallization of HAp occurs at 635 degrees C with an activation energy of 62.7--72.2 kcalmol(-1).