Porous Cu(I) Triazolate Framework and Derived Hybrid Membrane with Exceptionally High Sensing Efficiency for Gaseous Oxygen

Phosphorescent complexes of precious metal ions are widely studied as optical sensing materials for molecular oxygen. Combining the advantages of luminescent complexes and porous matrixes, porous coordination polymers show great potential for oxygen‐sensing, although their sensitivity, requirement of precious metal, and device fabrication remain challenging issues. In this work, the photoluminescence and oxygen‐sensing properties of the porous Cu(I) triazolate framework [Cu(detz)] (MAF‐2, Hdetz = 3,5‐diethyl‐1,2,4‐trizole) is studied in detail, which shows high chemical stability in moisture and water, very long phosphorescent lifetime (116 μs) and large Stokes shift (14 562 cm^?1), as well as considerable oxygen permeability (1.7 × 10^?11 mol cm^?1 s^?1 bar^?1) at ambient conditions, giving rise to exceptionally high luminescence quenching efficiency of 99.7% at 1 bar O₂ (I ₀/I ₁₀₀ = 356) with a perfectly linear Stern‐Volmer plot (K _SV = 356 bar^?1, R ² = 0.9998), fast response and good reversibility. Further, a counter‐diffusion crystal‐growth method was developed to fabricate MAF‐2 thin films protected by silicone rubbers as the first example of soft membrane oxygen sensor based on coordination polymer or metal‐organic framework, which exhibited extraordinary oxygen‐sensing performance (limit of detection = 0.047 mbar) and outstanding mechanical property, as well as outstanding chemical stability even in an acidic atmosphere.     

Self‐Assembly of Ferromagnetic Organic–Inorganic Perovskite‐Like Films

Perovskite‐based organic–inorganic hybrids hold great potential as active layers in electronics or optoelectronics or as components of biosensors. However, many of these applications require thin films grown with good control over structure and thickness—a major challenge that needs to be addressed. The work presented here is an effort towards this goal and concerns the layer‐by‐layer deposition at ambient conditions of ferromagnetic organic–inorganic hybrids consisting of alternating CuCl₄‐octahedra and organic layers. The Langmuir‐Blodgett technique used to assemble these structures provides intrinsic control over the molecular organization and film thickness down to the molecular level. Magnetic characterization reveals that the coercive field for these thin films is larger than that for solution‐grown layered bulk crystals. The strategy presented here suggests a promising cost effective route to facilitate the excellently controlled growth of sophisticated materials on a wide variety of substrates that have properties relevant for the high density storage media and spintronic devices.     

Isomeric Routes to Schiff‐Base Single‐layered Covalent Organic Frameworks

With graphene‐like topology and designable functional moieties, single‐layered covalent organic frameworks (sCOFs) have attracted enormous interest for both fundamental research and application prospects. As the growth of sCOFs involves the assembly and reaction of precursors in a spatial defined manner, it is of great importance to understand the kinetics of sCOFs formation. Although several large families of sCOFs and bulk COF materials based on different coupling reactions have been reported, the synthesis of isomeric sCOFs by exchanging the coupling reaction moieties on precursors has been barely explored. Herein, a series of isomeric sCOFs based on Schiff‐base reaction is designed to understand the effect of monomer structure on the growth kinetics of sCOFs. The distinctly different local packing motifs in the mixed assemblies for the two isomeric routes closely resemble to those in the assemblies of monomers, which affect the structural evolution process for highly ordered imine‐linked sCOFs. In addition, surface diffusion of monomers and the molecule‐substrate interaction, which is tunable by reaction temperature, also play an important role in structural evolutions. This study highlights the important roles of monomer structure and reaction temperature in the design and synthesis of covalent bond connected functional nanoporous networks.     

Nanoporous metal organic framework materials for smart applications

Abstract

This review is concerned with the recent advances in metal organic framework (MOF) materials. We highlight the unique combination of physicochemical and thermomechanical characteristics associated with MOF-type materials and illustrate emergent applications in three challenging technological sectors: energy, environmental remediation and biomedicine. MOFs represent an exciting new class of nanoporous crystalline solids constituting metal ions/clusters and multifunctional organic linkages, which self-assemble at molecular level to generate a plethora of ordered 3D framework materials. The most intriguing feature of a MOF lies in its exceptionally large surface area, far surpassing those of the best activated carbons and zeolites. Next generation multifunctional materials encompassing MOF based thin films, coatings, membranes and nanocomposites have potential for exploitation in an immense array of unconventional applications and smart devices. We pinpoint the key technological challenges and basic scientific questions to be addressed, so as to fulfil the translational potential for bringing MOFs from the laboratory into commercial applications.     

Coupling climate and hydrological models: Interoperability through Web Services

Understanding regional-scale water resource systems requires understanding coupled hydrologic and climate interactions. The traditional approach in the hydrologic sciences and engineering fields has been to either treat the atmosphere as a forcing condition on the hydrologic model, or to adopt a specific hydrologic model design in order to be interoperable with a climate model. We propose here a different approach that follows a service-oriented architecture and uses standard interfaces and tools: the Earth System Modeling Framework (ESMF) from the weather and climate community and the Open Modeling Interface (OpenMI) from the hydrologic community. A novel technical challenge of this work is that the climate model runs on a high performance computer and the hydrologic model runs on a personal computer. In order to complete a two-way coupling, issues with security and job scheduling had to be overcome. The resulting application demonstrates interoperability across disciplinary boundaries and has the potential to address emerging questions about climate impacts on local water resource systems. The approach also has the potential to be adapted for other climate impacts applications that involve different communities, multiple frameworks, and models running on different computing platforms. We present along with the results of our coupled modeling system a scaling analysis that indicates how the system will behave as geographic extents and model resolutions are changed to address regional-scale water resources management problems.     

Forum A historical context for theories underpinning the production of the built environment

The quest for ‘theory’ in the Building Research & Information special issue ‘Developing Theories of the Built Environment’ (36(3) 2008) needs to be understood within a larger historical and political context. It would benefit from engaging with a rich vein of work on the production of the built environment over the last 30 years. Theory inherently develops in the political context in which it exists; if it fails to do so, it may be dangerous. This commentary traces the intellectual underpinning concerned with understanding the process of change in the built environment, particularly the result of changes in social relations and the social labour process. The production of the built environment is seen as encompassing all the social processes concerned with producing the built environment, built products, buildings and infrastructure, and out of natural resources, whilst consumption is applied to all the processes involved in consuming these, including the well-being of tenants. And between these are situated the processes of exchange, distribution, and circulation, involving complex webs of relations between developers, builders, and landlords and landowners. The challenge is not only to engage and learn from past work, but also to state explicitly what is currently driving the need for a theory (or set of theories).

La quête de la « théorie » dans ce numéro spécial de Building Research & Information consacré aux théories du développement du milieu bâti (volume 36(3), 2008) doit être comprise dans un contexte historique et politique plus large. Elle aurait intérêt à s'appuyer sur les nombreux travaux concernant la production du cadre bâti publiés au cours de ces 30 dernières années. La théorie se développe, de manière inhérente, dans le contexte politique dans lequel elle existe; dans le cas contraire, la situation pourrait devenir dangereuse. Cet article analyse le raisonnement intellectuel sous-jacent concernant la compréhension du processus de changement dans le milieu bâti, notamment les conséquences des changements dans les relations sociales et dans le processus social du travail. La production du cadre bâti est considérée comme englobant tous les processus sociaux liés à la production du cadre bâti, des produits de construction, des bâtiments et des infrastructures et aux ressources naturelles alors que la consommation s'applique à tous les processus qui entrent en jeu dans la consommation de ceux-ci, y compris le bien-être des occupants. Entre ces deux notions, on trouve les processus d'échange, de distribution et de circulation qui font intervenir des réseaux de relations entre promoteurs, constructeurs, bailleurs et propriétaires fonciers. La difficulté ne vient pas seulement du fait qu'il faut tirer profit des travaux et de l'expérience passés mais qu'il faut également expliquer ce qui motive aujourd'hui la nécessité d'une théorie (ou d'un ensemble de théories).

Mots clés: cadre bâti, cadres conceptuels, consommation, processus de travail, cadre politique, production, relations sociales