Deterministic control of surface mounted metal–organic framework growth orientation on metallic and insulating surfaces

Vello, Tatiana P.; Strauss, Mathias; Costa, Carlos Alberto Rodrigues; Correa, Carlos; Bufon, Carlos César Bof

doi:10.1039/c9cp05717j

Cited by 21 publications

(64 citation statements)

References 49 publications

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“…360 The head group and the packing of the SAM also controls orientation of the resulting MOF or CP. 363 However, most studies have only focused on the out-of-plane orientation. Hence, heteroepitaxial methods that use oriented hydroxide precursors matching the MOF's lattice parameters have been developed to control both in-plane and out-of-plane orientations.…”

Section: Sequential Growth By Layer-by-layer/liquid Phase Epitaxymentioning

confidence: 99%

Electrical conductivity and magnetic bistability in metal–organic frameworks and coordination polymers: charge transport and spin crossover at the nanoscale

2020

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Section: Sequential Growth By Layer-by-layer/liquid Phase Epitaxymentioning

confidence: 99%

Electrical conductivity and magnetic bistability in metal–organic frameworks and coordination polymers: charge transport and spin crossover at the nanoscale

2020

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“…The step‐by‐step HKUST‐1 growth was performed as described earlier. [ 1,2 ] The grazing incidence X‐ray diffraction (GIXRD) pattern shown in Figure 1f and Figure S4 (Supporting Information) reveals the presence of crystalline HKUST‐1 thin films. [ 1,2,6 ] Well‐orientated HKUST‐1 films have been reported on COOH‐terminated organic surfaces.…”

Section: Resultsmentioning

confidence: 99%

“…SURMOFs are grown on functionalized surfaces using a layer‐by‐layer process. [ 1 ] The SURMOF approach provides highly orientated, monolithic, and homogenous MOF films with adjustable thickness firmly grafted to desired surfaces, [ 2 ] thus outperforming other forms of MOF thin films. SURMOFs have good mechanical flexibility, [ 3 ] high versatility, and are well suited for integration into devices and systems in various application fields.…”

Section: Introductionmentioning

confidence: 99%

“…HKUST‐1 (Hong Kong University of Science and Technology) is a widely explored MOF that is well suited for the layer‐by‐layer process, allowing the growth of high‐quality SURMOF films at ambient conditions a large variety of solid substrates. [ 2 ] The electronic structure of HKUST‐1 SURMOF is susceptible to the presence of water, causing the appearance of additional states in the bandgap region. [ 6 ] Thus, by adequately tailoring external conditioning parameters, the band‐structure of HKUST‐1 SURMOFs can be designed to explore unprecedented quantum electronic tunneling phenomena.…”

Section: Introductionmentioning

confidence: 99%

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Room‐Temperature Negative Differential Resistance in Surface‐Supported Metal‐Organic Framework Vertical Heterojunctions

Albano

Camargo

Schleder

et al. 2021

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The advances of surface‐supported metal‐organic framework (SURMOF) thin‐film synthesis have provided a novel strategy for effectively integrating metal‐organic framework (MOF) structures into electronic devices. The considerable potential of SURMOFs for electronics results from their low cost, high versatility, and good mechanical flexibility. Here, the first observation of room‐temperature negative differential resistance (NDR) in SURMOF vertical heterojunctions is reported. By employing the rolled‐up nanomembrane approach, highly porous sub‐15 nm thick HKUST‐1 films are integrated into a functional device. The NDR is tailored by precisely controlling the relative humidity (RH) around the device and the applied electric field. The peak‐to‐valley current ratio (PVCR) of about two is obtained for low voltages (<2 V). A transition from a metastable state to a field emission‐like tunneling is responsible for the NDR effect. The results are interpreted through band diagram analysis, density functional theory (DFT) calculations, and ab initio molecular dynamics simulations for quasisaturated water conditions. Furthermore, a low‐voltage ternary inverter as a multivalued logic (MVL) application is demonstrated. These findings point out new advances in employing unprecedented physical effects in SURMOF heterojunctions, projecting these hybrid structures toward the future generation of scalable functional devices.

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“…[56] Additionally, the choice of headgroup chemistry will determine the orientation of the SURMOF. [77,78] This can be explained by considering the paddlewheel SBU of HKUST-1, where the copper ions possess two different binding positions (equatorial and axial). [44] The SAM headgroups can be tailored to mimic both of these bonding conformations (Figure 1.3).…”

Section: Surface-anchored Metal-organic Frame-workmentioning

confidence: 99%

In Situ Nano-Spectroscopy on Surface-Anchored Metal-Organic Frameworks

Delen¹

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Metal-Organic Frameworks, or MOFs, are a relatively new class of materials that consists of both metallic and organic moieties. [1,[15][16][17] The MOF materials class is part of the Porous Coordination Polymer (PCP) family. [18,19] Per definition, MOFs are composed of repeating coordination entities extending in 1, 2, or 3 dimensions. [20] Therefore, to compose structures stretching along these dimensions, the organic moieties are required to be polydentate linkers, linking the metal nodes into an extended network often resulting in high crystallinity and large porosity. [21] However, to properly describe MOF structures, it is insufficient to regard the metal nodes and organic linkers as the sole repeating entities as they do not contain any information to describe the resulting MOF topology.To better describe, and predict, the structure of MOFs, the concept of secondary building units (SBUs) was introduced. [22,23] As opposed to the flexible bonds between a single metal and organic linker, SBUs are coordinated clusters of di-, tri-, and tetranuclear metal-organic clusters. These clusters are molecular units with defined structure, shape, and direction which dictate the structure, shape, and direction of MOFs. Not only are they useful in predicting the topology of a MOF, but they are also excellent predictors of MOF robustness. [24] This becomes especially important when considering (permanent) porosity in MOFs after solvent removal, and thus their functionality. [25] A characteristic of MOFs is that they typically exhibit high porosity (in the order of hundreds to thousands of m 2 /g) since pores with a size proportional to the linker length are created during synthesis. [26,27] As a result, there are continuing efforts to increase reported porosities by using increasingly long linkers. [28,29] However, a MOF is only porous when the remaining solvent molecules are evacuated after synthesis. In practice, many MOF structures collapse upon this evacuation step. [30] The use of rigid SBUs, such as highly connected oxo-clusters, impart higher stability, and lead to permanent porosity. [31] This porosity is expressed as pores connecting the MOF surfaces to internal cages, as well as 1, 2, and 3D channel systems. [27] This large and ordered porosity goes hand-in-hand with a second typical (yet not necessary) characteristic of MOFs: their high crystallinity. [32] A third characteristic of MOFs is that their functionality is highly tunable as the choices for metals and linkers are virtually infinitely variable. [33] Specific examples of variable functionality are the incorporation of Coordinatively Unsaturated (metal) Sites (CUS), also characterized as Lewis acid sites, or the incorporation of linkers with Bronsted acid/base sites. [34,35] The three combined characteristics of MOFs lead to the conclusion that MOFs are very interesting materials in applications depending on their interaction with gaseous guest molecules, such as gas sorption, gas separation, gas sensing, and gas conversion (catalysis). ...

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Deterministic control of surface mounted metal–organic framework growth orientation on metallic and insulating surfaces

Abstract: Surface-Mounted Metal–Organic Frameworks (SURMOFs) growth orientation in [100] or [111] can be deterministically controlled by the SAM chain length, regardless of the surface nature (metallic or insulating).

Cited by 21 publications

References 49 publications

Electrical conductivity and magnetic bistability in metal–organic frameworks and coordination polymers: charge transport and spin crossover at the nanoscale

Electrical conductivity and magnetic bistability in metal–organic frameworks and coordination polymers: charge transport and spin crossover at the nanoscale

Room‐Temperature Negative Differential Resistance in Surface‐Supported Metal‐Organic Framework Vertical Heterojunctions

In Situ Nano-Spectroscopy on Surface-Anchored Metal-Organic Frameworks

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