Hai-Long Jiang

From Metal–Organic Framework to Nanoporous Carbon: Toward a Very High Surface Area and Hydrogen Uptake

In this work, with a zeolite-type metal-organic framework as both a precursor and a template and furfuryl alcohol as a second precursor, nanoporous carbon material has been prepared with an unexpectedly high surface area (3405 m(2)/g, BET method) and considerable hydrogen storage capacity (2.77 wt % at 77 K and 1 atm) as well as good electrochemical properties as an electrode material for electric double layer capacitors. The pore structure and surface area of the resultant carbon materials can be tuned simply by changing the calcination temperature.

Synergistic Catalysis of Au@Ag Core—Shell Nanoparticles Stabilized on Metal—Organic Framework

For the first time, this work presents Au@Ag core-shell nanoparticles (NPs) immobilized on a metal-organic framework (MOF) by a sequential deposition-reduction method. The small-size Au@Ag NPs reveal the restriction effects of the pore/surface structure in the MOF. The modulation of the Au/Ag ratio can tune the composition and a reversed Au/Ag deposition sequence changes the structure of Au-Ag NPs, while a posttreatment process transforms the core-shell NPs to a AuAg alloy. Catalytic studies show a strong bimetallic synergistic effect of core-shell structured Au@Ag NPs, which have much higher catalytic activities than alloy and monometallic NPs.

Zirconium-Metalloporphyrin PCN-222: Mesoporous Metal–Organic Frameworks with Ultrahigh Stability as Biomimetic Catalysts†

In nature, metalloporphyrins are well known for performing many biological functions in aqueous media, such as light harvesting, oxygen transportation, and catalysis. Heme, the iron–porphyrin derivative, is the cofactor for many enzyme/ protein families, including peroxidases, cytochromes, hemoglobins, and myoglobins. Using synthetic systems to mimic natural enzymes with high catalytic activity and substrate selectivity has been a sought-after goal in the last decade. Direct application of a heme as an oxidation catalyst in aqueous solution is usually challenging due to the formation of catalytically inactive dimers and catalyst self-destruction in the oxidizing reaction media. One promising approach is to load heme on supports, such as zeolites, clays, nanoparticles, hydrogels, or carbon materials, a practice which inevitably dilutes the density of active sites. An alternative approach is to protect the heme center by modifying the porphyrin to produce dendrimers or molecular crystals, which is a synthetically demanding method. Herein, we propose a unique strategy employing heme-like active centers as structural motifs for the assembly of highly stable porous materials, which should possess well-defined mesochannels and ultrahigh stability in aqueous solution. Metal-organic frameworks (MOFs) are a new class of crystalline porous materials with fascinating structures and intriguing properties, such as permanent porosity, high surface area, and uniform open cavities. The availability of various building blocks consisting of metals and organic linkers makes it possible to construct MOFs with unique properties for diverse applications. However, these desirable features of MOFs have rarely been applied to an enzymatic mimic, especially for catalysis in an aqueous medium, despite the fact that the assembly of ligands bearing high-density active sites into 3D frameworks may provide an ideal system to both enhance the catalytic activity and protect the cofactors. One of the main reasons is the lack of water-stable MOFs containing redox-active metal centers. Furthermore, most MOFs are microporous (pore size< 2 nm). Although they are suitable for gas storage, the small pore size slows down diffusion and limits the access of large substrate molecules to the active sites inside a MOF. Therefore, MOFs with mesopores, accessible redox sites, and ultrahigh stability, especially in aqueous media, are indispensible for any successful biomimetic attempt. Herein we have employed Fe-TCPP (TCPP= tetrakis(4carboxyphenyl)porphyrin) as a heme-like ligand and chosen highly stable Zr6 clusters as nodes for the assembly of stable Zr-MOFs. With carefully selected starting materials, we have successfully constructed a 3D heme-like MOF, designated as PCN-222(Fe) (Figure 1; PCN= porous coordination net-

Non-, Micro-, and Mesoporous Metal−Organic Framework Isomers: Reversible Transformation, Fluorescence Sensing, and Large Molecule Separation

For the first time, three novel metal-organic framework (MOF) isomers with hierarchical channel sizes of nonpore or micropore or mesopore were successfully prepared by simply controlling the amounts of solvent or/and reaction temperatures/time. Strikingly, we have demonstrated the reversible transformation between the microporous and mesoporous MOFs triggered by solvent or/and temperature perturbation. The desolvated microporous MOF has been evaluated to be a promising luminescent probe for detecting small molecules, and the mesoporous MOF could be the stationary phase in high-performance liquid chromatography (HPLC) for size-exclusion separation of large dye molecules.

Au@ZIF-8: CO oxidation over gold nanoparticles deposited to metal-organic framework.

Gold nanoparticles (NPs) were deposited to a zeolite-type metal-organic framework (MOF) by a simple solid grinding method. A catalyst, Au@ZIF-8, represents the first example of an active catalyst in CO oxidation by using a MOF as a novel support for noble metal NPs. The catalytic activity for CO oxidation is improved along with increasing Au loadings, and the highest catalytic activity is obtained for 5.0 wt % Au@ZIF-8, which presents half conversion of CO at approximately 170 degrees C. Gold NPs are close to being monodisperse and have no aggregation during catalytic reaction, and the catalytic activity is reproducible.

Synergistic Catalysis of Metal–Organic Framework-Immobilized Au–Pd Nanoparticles in Dehydrogenation of Formic Acid for Chemical Hydrogen Storage

Bimetallic Au-Pd nanoparticles (NPs) were successfully immobilized in the metal-organic frameworks (MOFs) MIL-101 and ethylenediamine (ED)-grafted MIL-101 (ED-MIL-101) using a simple liquid impregnation method. The resulting composites, Au-Pd/MIL-101 and Au-Pd/ED-MIL-101, represent the first highly active MOF-immobilized metal catalysts for the complete conversion of formic acid to high-quality hydrogen at a convenient temperature for chemical hydrogen storage. Au-Pd NPs with strong bimetallic synergistic effects have a much higher catalytic activity and a higher tolerance with respect to CO poisoning than monometallic Au and Pd counterparts.

From Bimetallic Metal‐Organic Framework to Porous Carbon: High Surface Area and Multicomponent Active Dopants for Excellent Electrocatalysis

Bimetallic metal-organic frameworks are rationally synthesized as templates and employed for porous carbons with retained morphology, high graphitization degree, hierarchical porosity, high surface area, CoNx moiety and uniform N/Co dopant by pyrolysis. The optimized carbon with additional phosphorus dopant exhibits excellent electrocatalytic performance for the oxygen reduction reaction, which is much better than the benchmark Pt/C in alkaline media.

Construction of Ultrastable Porphyrin Zr Metal–Organic Frameworks through Linker Elimination

A series of highly stable MOFs with 3-D nanochannels, namely PCN-224 (no metal, Ni, Co, Fe), have been assembled with six-connected Zr6 cluster and metalloporphyrins by a linker-elimination strategy. The PCN-224 series not only exhibits the highest BET surface area (2600 m(2)/g) among all the reported porphyrinic MOFs but also remains intact in pH = 0 to pH = 11 aqueous solution. Remarkably, PCN-224(Co) exhibits high catalytic activity for the CO2/propylene oxide coupling reaction and can be used as a recoverable heterogeneous catalyst.

An Exceptionally Stable, Porphyrinic Zr Metal–Organic Framework Exhibiting pH-Dependent Fluorescence

A reaction between a Zr(IV) salt and a porphyrinic tetracarboxylic acid leads to a metal-organic framework (MOF) with two types of open channels, representing a MOF featuring a (4,8)-connected sqc net. The MOF remains intact in both boiling water and aqueous solutions with pH ranging from 1 to 11, a remarkably extensive pH range that a MOF can sustain. Given its exceptional stability and pH-dependent fluorescent intensity, the MOF can potentially be applied in fluorescent pH sensing.

Recent progress in synergistic catalysis over heterometallic nanoparticles

Heterometallic nanoparticles (NPs) have been emerging as a type of important catalyst. Bimetallic NPs with alloyed and core–shell structures have higher activities than monometallic counterparts in catalysis due to the synergistic effects between the two metals. Compared to the straightforward synthesis of bimetallic alloy NPs, the preparation strategies for bimetallic core–shell NPs are flexible and diversified. In addition, synergistic catalysis over trimetallic and multimetallic NPs has also received considerable interest in recent years. In this feature article, we provide an overview of the recent developments of heterometallic NPs for improved catalytic performance.