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[资源] Acc. Chem. Res.最新综述：无定型的金属——有机骨架

Amorphous Metal − Organic Frameworks 共8页引文38篇
Thomas D. Bennett * and Anthony K. Cheetham *
Department of Materials Science and Metallurgy, University of Cambridge, 27 Charles Babbage Road, Cambridge CB3 0FS, United Kingdom

CONSPECTUS: Crystalline metal − organic frameworks (MOFs) are porous frameworks comprising an in ﬁ nite array of metal nodes connected by organic linkers. The number of novel MOF structures reported per year is now in excess of 6000, despite signi ﬁ cant increases in the complexity of both component units and molecular networks. Their regularly repeating structures give rise to chemically variable porous architectures, which have been
studied extensively due to their sorption and separation potential. More recently, catalytic applications have been proposed that make use of their chemical tunability, while reports of negative linear compressibility and negative thermal expansion have further expanded interest in the ﬁ eld.
Amorphous metal − organic frameworks (aMOFs) retain the basic building blocks and connectivity of their crystalline
counterparts, though they lack any long-range periodic order. Aperiodic arrangements of atoms result in their X-ray di ﬀ raction
patterns being dominated by broad “ humps ” caused by di ﬀ use scattering and thus they are largely indistinguishable from one
another. Amorphous MOFs o ﬀ er many exciting opportunities for practical application, either as novel functional materials
themselves or facilitating other processes, though the domain is largely unexplored (total aMOF reported structures amounting
to under 30).
Speci ﬁ cally, the use of crystalline MOFs to detect harmful guest species before subsequent stress-induced collapse and guest
immobilization is of considerable interest, while functional luminescent and optically active glass-like materials may also be
prepared in this manner. The ion transporting capacity of crystalline MOFs might be improved during partial structural collapse,
while there are possibilities of preparing superstrong glasses and hybrid liquids during thermal amorphization. The tuning of
release times of MOF drug delivery vehicles by partial structural collapse may be possible, and aMOFs are often more
mechanically robust than crystalline materials, which is of importance for industrial applications.
In this Account, we describe the preparation of aMOFs by introduction of disorder into their parent crystalline frameworks
through heating, pressure (both hydrostatic and nonhydrostatic), and ball-milling. The main method of characterizing these
amorphous materials (analysis of the pair distribution function) is summarized, alongside complementary techniques such as
Raman spectroscopy. Detailed investigations into their properties (both chemical and mechanical) are compiled and compared
with those of crystalline MOFs, while the impact of the ﬁ eld on the processing techniques used for crystalline MOF powders is
also assessed. Crucially, the bene ﬁ ts amorphization may bring to existing proposed MOF applications are detailed, alongside the
possibilities and research directions a ﬀ orded by the combination of the unique properties of the amorphous domain with the
versatility of MOF chemistry.

Biography
Thomas D. Bennett was born in South Shields, U.K. (1986). He read the Natural Sciences Tripos at the University of Cambridge, specializing in Chemistry, where he completed an M.Sci. project on hybrid framework materials under Paul T. Wood. After moving to the Department of Materials Science and Metallurgy, he completed a Ph.D. on the thermomechanical properties of zeolitic imidazolate frameworks, under Professor Anthony Cheetham. In 2009, he was elected to a honorary research fellowship at the Ras Al Khaimah center for advanced materials (RAK-CAM), and in 2012, he won the Panalytical prize for an outstanding contribution to X-ray diffraction. Thomas is currently a Research Fellow at Trinity Hall, University of Cambridge, and focuses on the synthesis, structure, properties, and applications of amorphous hybrid frameworks
Biography
Tony Cheetham obtained his D.Phil. at Oxford in 1971 and joined the chemistry faculty in 1974. In 1992, he took up the Directorship of the new Materials Research Laboratory at the University of California at Santa Barbara, before moving to Cambridge in 2007 to become the Goldsmiths’ Professor of Materials Science. Cheetham is a Fellow of the Royal Society (1994) and several other academies and has received numerous major awards for his work in the field of inorganic and materials chemistry, including a Chemical Pioneer Award from the American Institute of Chemists (2014). He became the Treasurer and Vice-President of the Royal Society at the end of November 2012.

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