Among the large family of metal–organic frameworks (MOFs), Zr-based MOFs, which exhibit rich structure types, outstanding stability, intriguing properties and functions, are foreseen as one of the most promising MOF materials for practical applications. Although this specific type of MOF is still in its early stage of development, significant progress has been made in recent years. Herein, advances in Zr-MOFs since 2008 are summarized and reviewed from three aspects: design and synthesis, structure, and applications. Four synthesis strategies implemented in building and/or modifying Zr-MOFs as well as their scale-up preparation under green and industrially feasible conditions are illustrated first. Zr-MOFs with various structural types are then classified and discussed in terms of different Zr-based secondary building units and organic ligands. Finally, applications of Zr-MOFs in catalysis, molecule adsorption and separation, drug delivery, and fluorescence sensing, and as porous carriers are highlighted. Such a review based on a specific type of MOF is expected to provide guidance for the in-depth investigation of MOFs towards practical applications.

Zr-based metal-organic frameworks: design, synthesis, structure, and applications.

The modification of surfaces by the deposition of a robust overlayer provides an excellent handle with which to tune the properties of a bulk substrate to those of interest. Such control over the surface properties becomes increasingly important with the continuing efforts at down-sizing the active components in optoelectronic devices, and the corresponding increase in the surface area/volume ratio. Relevant properties to tune include the degree to which a surface is wetted by water or oil. Analogously, for biosensing applications there is an increasing interest in so-called “romantic surfaces”: surfaces that repel all biological entities, apart from one, to which it binds strongly. Such systems require both long lasting and highly specific tuning of the surface properties. This Review presents one approach to obtain robust surface modifications of the surface of oxides, namely the covalent attachment of monolayers.

Covalent surface modification of oxide surfaces.

Cleḿence Queffeĺec,† Marc Petit,†,‡ Pascal Janvier,† D. Andrew Knight, and Bruno Bujoli*,† †LUNAM Universite,́ CNRS, UMR 6230, Chimie Et Interdisciplinarite:́ Synthes̀e Analyse Modeĺisation (CEISAM), UFR Sciences et Techniques, 2, rue de la Houssinier̀e, BP 92208, 44322 NANTES Cedex 3, France ‡Universite ́ Pierre et Marie Curie (UPMC), CNRS, UMR7201, Institut Parisien De Chimie Molećulaire (IPCM), 4 place Jussieu, 75252 Paris Cedex 05, France Chemistry Department, Florida Institute of Technology, 150 West University Boulevard, Melbourne, Florida 32901, United States

Surface modification using phosphonic acids and esters.

Nanomaterials have emerged as an amazing class of materials that consists of a broad spectrum of examples with at least one dimension in the range of 1 to 100 nm. Exceptionally high surface areas can be achieved through the rational design of nanomaterials. Nanomaterials can be produced with outstanding magnetic, electrical, optical, mechanical, and catalytic properties that are substantially different from their bulk counterparts. The nanomaterial properties can be tuned as desired via precisely controlling the size, shape, synthesis conditions, and appropriate functionalization. This review discusses a brief history of nanomaterials and their use throughout history to trigger advances in nanotechnology development. In particular, we describe and define various terms relating to nanomaterials. Various nanomaterial synthesis methods, including top-down and bottom-up approaches, are discussed. The unique features of nanomaterials are highlighted throughout the review. This review describes advances in nanomaterials, specifically fullerenes, carbon nanotubes, graphene, carbon quantum dots, nanodiamonds, carbon nanohorns, nanoporous materials, core–shell nanoparticles, silicene, antimonene, MXenes, 2D MOF nanosheets, boron nitride nanosheets, layered double hydroxides, and metal-based nanomaterials. Finally, we conclude by discussing challenges and future perspectives relating to nanomaterials.

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Nanomaterials: a review of synthesis methods, properties, recent progress, and challenges

The synthesis of renewable fuels from abundant water or the greenhouse gas CO2 is a major step toward creating sustainable and scalable energy storage technologies. In the last few decades, much attention has focused on the development of nonprecious metal-based catalysts and, in more recent years, their integration in solid-state support materials and devices that operate in water. This review surveys the literature on 3d metal-based molecular catalysts and focuses on their immobilization on heterogeneous solid-state supports for electro-, photo-, and photoelectrocatalytic synthesis of fuels in aqueous media. The first sections highlight benchmark homogeneous systems using proton and CO2 reducing 3d transition metal catalysts as well as commonly employed methods for catalyst immobilization, including a discussion of supporting materials and anchoring groups. The subsequent sections elaborate on productive associations between molecular catalysts and a wide range of substrates based on carbon, quantum dot...

Electro- and Solar-Driven Fuel Synthesis with First Row Transition Metal Complexes.

Metal ion complexes are playing an increasing role in the development of antimicrobials. We review here the antimicrobial properties of cobalt coordination complexes in oxidation state 3+. In addition to reviewing the cobalt complexes containing polydentate donor ligands, we also focus on the antimicrobial activity of the homoleptic [Co(NH3)6]3+ ion.

Cobalt Complexes as Antiviral and Antibacterial Agents

Kinetics, stoichiometry, and products of the oxidation of trimethoprim (TMP), one of the most commonly detected antibacterial agents in surface waters and municipal wastewaters, by ferrate(VI) (Fe(VI)) were determined. The pH dependent second-order rate constants of the reactions of Fe(VI) with TMP were examined using acid–base properties of Fe(VI) and TMP. The kinetics of reactions of diaminopyrimidine (DAP) and trimethoxytoluene (TMT) with Fe(VI) were also determined to understand the reactivity of Fe(VI) with TMP. Oxidation products of the reactions of Fe(VI) with TMP and DAP were identified by liquid chromatography-tandem mass spectrometry (LC–MS/MS). Reaction pathways of oxidation of TMP by Fe(VI) are proposed to demonstrate the cleavage of the TMP molecule to ultimately result in 3,4,5,-trimethoxybenzaldehyde and 2,4-dinitropyrimidine as among the final identified products. The oxidized products mixture exhibited no antibacterial activity against E. coli after complete consumption of TMP. Removal of...

Oxidation of trimethoprim by ferrate(VI): kinetics, products, and antibacterial activity.

Antiviral properties of cobalt(III)-complexes.

Synthesis, structure, and reactivity of chiral rhenium imine and methyleneamido complexes of the formulas [(.eta.5-C5H5)Re(NO)(PPh3)(.eta.1-NR'':CRR')]+ TfO- and (.eta.5-C5H5)Re(NO)(PPh3)(N:CRR')

D. Andrew Knight

Papers

Surface modification using phosphonic acids and esters.

Cobalt Complexes as Antiviral and Antibacterial Agents

Oxidation of trimethoprim by ferrate(VI): kinetics, products, and antibacterial activity.

Antiviral properties of cobalt(III)-complexes.

Synthesis, structure, and reactivity of chiral rhenium imine and methyleneamido complexes of the formulas [(.eta.5-C5H5)Re(NO)(PPh3)(.eta.1-NR'':CRR')]+ TfO- and (.eta.5-C5H5)Re(NO)(PPh3)(N:CRR')