Towards scalable and controlled synthesis of metal–organic framework materials using continuous flow reactors

Dunne, Peter W.; Lester, Edward; Walton, Richard I.

doi:10.1039/c6re00107f

Cited by 68 publications

(37 citation statements)

References 53 publications

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“…Our results show that UiO‐66‐MSBDC( y ) catalysts are highly promising for scale‐up because they operate under aqueous conditions and are recyclable, and furthermore, their synthesis is simple and short and does not require toxic and corrosive conditions. Scaled‐up synthesis of the MOFs by using continuous flow reactors, often using water as a reaction medium, makes this a realistic prospect . Enzymes including metal centers and basic histidine moieties possessing multifunctional capabilities are nature's catalysts, and they provide high selectivity at the expense of slow reactions and sensitive operational systems.…”

Section: Figurementioning

confidence: 99%

Exceptionally Efficient and Recyclable Heterogeneous Metal–Organic Framework Catalyst for Glucose Isomerization in Water

et al. 2018

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Heterogeneous catalysts are desired for the conversion of glucose, the most abundant sugar in renewable biomass, but presently their synthesis requires highly toxic chemicals with long synthesis times. We report the conversion of glucose into fructose and 5‐hydroxymethylfurfural on a heterogeneous catalyst that is stable and selective and operates in the most environmentally benign solvent, water. We used a bifunctional solid with Lewis and Brønsted acid sites by partially replacing the organic linker of the zirconium organic framework UiO‐66 with 2‐monosulfo‐benzene‐1,4‐dicarboxylate. This catalyst showed high product selectivity (90 %) to 5‐hydroxymethylfurfural and fructose at 140 °C in water after a reaction time of 3 h. It was recyclable and showed only a minor loss in activity after the third recycle, offering a realistic solution for the bottleneck glucose isomerization reaction for scale‐up and industrial application of biomass utilization.

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Section: Figurementioning

confidence: 99%

Exceptionally Efficient and Recyclable Heterogeneous Metal–Organic Framework Catalyst for Glucose Isomerization in Water

et al. 2018

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“…[6] Also,t oh elp speed up the discovery and optimization of new materials,h igh-throughput hydrothermal methods which allow the systematic investigation of the reaction parameters have been developed. [9] Despite these advances,c onventional hydrothermal syntheses are still usually carried out under one-pot, single step conditions,w hich precludes the exploration of multi-step reactions or more complex reaction conditions.T his limits the ability to introduce synthetic complexity,whereby the composition of the reaction mixture can be changed under the reaction conditions without interruption. [9] Despite these advances,c onventional hydrothermal syntheses are still usually carried out under one-pot, single step conditions,w hich precludes the exploration of multi-step reactions or more complex reaction conditions.T his limits the ability to introduce synthetic complexity,whereby the composition of the reaction mixture can be changed under the reaction conditions without interruption.…”

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“…[7,8] In addition, continuous flow hydrothermal techniques have been introduced for scalable synthesis. [9] Despite these advances,c onventional hydrothermal syntheses are still usually carried out under one-pot, single step conditions,w hich precludes the exploration of multi-step reactions or more complex reaction conditions.T his limits the ability to introduce synthetic complexity,whereby the composition of the reaction mixture can be changed under the reaction conditions without interruption. Some approaches to multi-stage hydrothermal reactions do exist, however these are limited to bespoke designed flow systems which are beyond the capabilities and means of many researchers.…”

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Digital Control of Multistep Hydrothermal Synthesis by Using 3D Printed Reactionware for the Synthesis of Metal–Organic Frameworks

et al. 2018

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Hydrothermal‐synthesis‐based reactions are normally single step owing to the difficulty of manipulating reaction mixtures at high temperatures and pressures. Herein we demonstrate a simple, cheap, and modular approach to the design reactors consisting of partitioned chambers, to achieve multi‐step synthesis under hydrothermal conditions, in digitally defined reactionware produced by 3D printing. This approach increases the number of steps that can be performed sequentially and allows an increase in the options available for the control of hydrothermal reactions. The synthetic outcomes of the multi‐stage reactions can be explored by varying reaction compositions, number of reagents, reaction steps, and reaction times, and these can be tagged to the digital blueprint. To demonstrate the potential of this approach a series of polyoxometalate (POM)‐containing metal–organic frameworks (MOFs) unavailable by “one‐pot” methods were prepared as well as a set of new MOFs.

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“…Alternative synthesis methods such as liquid assisted grinding (LAG) and aqueous synthesis reduce cost by reducing solvent usage and provide cost projections in the range from $13 kg −1 to $36 kg −1 (representing 34-83% reductions) for scaled-up manufacture [113]. Scalable, continuous processes for manufacture have also been investigated [114][115][116][117]. The NU-125 MOF can be made in high yield on the gram-scale [83].…”

Section: Practical Implementationmentioning

confidence: 99%

Implementing Metal-Organic Frameworks for Natural Gas Storage

et al. 2019

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Methane can be stored by metal-organic frameworks (MOFs). However, there remain challenges in the implementation of MOFs for adsorbed natural gas (ANG) systems. These challenges include thermal management, storage capacity losses due to MOF packing and densification, and natural gas impurities. In this review, we discuss discoveries about how MOFs can be designed to address these three challenges. For example, Fe(bdp) (bdp 2− = 1,4-benzenedipyrazolate) was discovered to have intrinsic thermal management and released 41% less heat than HKUST-1 (HKUST = Hong Kong University of Science and Technology) during adsorption. Monolithic HKUST-1 was discovered to have a working capacity 259 cm 3 (STP) cm −3 (STP = standard temperature and pressure equivalent volume of methane per volume of the adsorbent material: T = 273.15 K, P = 101.325 kPa), which is a 50% improvement over any other previously reported experimental value and virtually matches the 2012 Department of Energy (Department of Energy = DOE) target of 263 cm 3 (STP) cm −3 after successful packing and densification. In the case of natural gas impurities, higher hydrocarbons and other molecules may poison or block active sites in MOFs, resulting in up to a 50% reduction of the deliverable energy. This reduction can be mitigated by pore engineering. of 9.2 MJ L −1 , which is 70% less than that of gasoline [2,15]. However, carrying an extremely pressurized tank raises safety concerns in vehicles in the case of accidents and has an energy cost associated with compression. Furthermore, CNG, which is the established and predominant technology for NGVs, has a driving range of 350-450 km as compared to 400-600 km for gasoline-powered vehicles [16]. Based on this, there is a need to develop gas storage technology beyond that which is already established in real life applications. Further improvements in natural gas storage for NGV technology should seek to improve driving range to decrease time at the pump and the corresponding number of required tank recharges. Increasing driving range would be helpful to implement the technology in areas where natural gas filling stations are not as abundant. In addition, the CNG tank that holds the fuel takes up cargo space and technological advancements that decrease the volume of the natural gas fuel tank are beneficial. Another approach to store natural gas is LNG, which has an energy density of 22.2 MJ L −1 . Some drawbacks of LNG are the energy and cost associated with liquefaction (−162 • C), which present major technological obstacles [17,18] Lastly natural gas can be stored as ANG. Fairly large volumetric capacities of 4-6 MJ L −1 at pressures of around 35 bar at room temperature for different adsorbents were achieved [19]. The presence of sorbent materials in high pressure tanks reduces the pressure requirement of the tanks, making storage and delivery safer and allows for the use of single-stage compressors. ANG may increase the driving range and decrease the volume required of the fuel tank to achieve a specific driving dis...

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Towards scalable and controlled synthesis of metal–organic framework materials using continuous flow reactors

Cited by 68 publications

References 53 publications

Exceptionally Efficient and Recyclable Heterogeneous Metal–Organic Framework Catalyst for Glucose Isomerization in Water

Exceptionally Efficient and Recyclable Heterogeneous Metal–Organic Framework Catalyst for Glucose Isomerization in Water

Digital Control of Multistep Hydrothermal Synthesis by Using 3D Printed Reactionware for the Synthesis of Metal–Organic Frameworks

Implementing Metal-Organic Frameworks for Natural Gas Storage

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