Synthesis and Metalation of Catechol-Functionalized Porous Organic Polymers

Weston, Mitchell H.; Farha, Omar K.; Hauser, Bernard A.; Hupp, Joseph T.; Nguyen, SonBinh T.

doi:10.1021/cm2034646

Cited by 99 publications

(93 citation statements)

References 34 publications

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“…Successful pre-and post-synthetic metalation reactions have been demonstrated for a limited numbers of porous organic polymers exhibiting bipyridine, salen, porphyrin, and catechol chelating moieties. [212][213][214][215] , respectively). Future work would benefit from the investigation of the relationship between metal ion coordination environment and H 2 adsorption in such materials.…”

mentioning

confidence: 98%

An assessment of strategies for the development of solid-state adsorbents for vehicular hydrogen storage

Allendorf

Hulvey

Gennett

et al. 2018

Energy Environ. Sci.

229

187

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Nanoporous adsorbents are a diverse category of solid-state materials that hold considerable promise for vehicular hydrogen storage. Although impressive storage capacities have been demonstrated for several materials, particularly at cryogenic temperatures, materials meeting all of the targets established by the U.S. Department of Energy have yet to be identified. In this Perspective, we provide an overview of the major known and proposed strategies for hydrogen adsorbents, with the aim of guiding ongoing research as well as future new storage concepts. The discussion of each strategy includes current relevant literature, strengths and weaknesses, and outstanding challenges that preclude implementation. We consider in particular metal-organic frameworks (MOFs), including surface area/volume tailoring, open metal sites, and the binding of multiple H 2 molecules to a single metal site. Two related classes of porous framework materials, covalent organic frameworks (COFs) and porous aromatic frameworks (PAFs), are also discussed, as are graphene and graphene oxide and doped porous carbons. We additionally introduce criteria for evaluating the merits of a particular materials design strategy. Computation has become an important tool in the discovery of new storage materials, and a brief introduction to the benefits and limitations of computational predictions of H 2 physisorption is therefore presented. Finally, considerations for the synthesis and characterization of hydrogen storage adsorbents are discussed. IntroductionStorage of hydrogen with sufficient gravimetric and volumetric capacity for vehicular use remains a significant obstacle to the widespread adoption of hydrogen fuel cell electric vehicles (FCEVs). Several FCEV models are now commercially available in limited locations around the world, and in these vehicles hydrogen is stored as a gas at room temperature with a fill Table 1 along with the current performance of 700 bar systems. These values pertain to the entire storage system, which includes the mass and volume of hydrogen in addition to the tank and associated balance-ofplant (BOP) components. Notably, it is physically impossible to meet the 2025 and ultimate volumetric capacity target with pressurized gas, as the density of H 2 gas at 700 bar and room temperature is just 40 g L À1 without accounting for the BOP.The search for solid-state H 2 storage materials that can supplant compressed gas systems has been ongoing for at least two decades. The development of a viable storage material Broader contextThe widespread use of hydrogen as a clean, sustainable energy carrier has the potential to provide several significant benefits, including a reduction in oil dependency and emissions, improved energy security and grid resiliency, and substantial economic opportunities across many sectors. Hydrogen-fueled vehicles are already appearing internationally, and one of the critical enabling technologies for increasing their availability is on-board hydrogen storage. Stakeholders in developing a hydrogen in...

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mentioning

confidence: 98%

An assessment of strategies for the development of solid-state adsorbents for vehicular hydrogen storage

Allendorf

Hulvey

Gennett

et al. 2018

Energy Environ. Sci.

229

187

View full text Add to dashboard Cite

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“…1) that features high surface area with densely populated yet highly accessible Hg(II) binding sites thereby affording high Hg(II) adsorption capacity; strong Hg(II) chelating groups that are well dispersed throughout the single-walled pore surface thus rendering high affinity for Hg(II) and efficient utilization of Hg(II) binding sites; large yet tunable pore size to enable fast yet controllable kinetics of Hg(II) adsorption; Hg(II) chelating groups that are covalently anchored to the backbone thus avoiding the leaching of binding sites; exceptional water/chemical stability facilitating regeneration/recyclability. Such mercury 'nano-trap' can be targeted by grafting desired Hg(II) chelating groups to the highly robust porous organic polymers (POPs) [35][36][37][38][39][40][41][42][43][44] that exhibit high surface areas, tunable pore sizes and high water/ chemical stabilities, via stepwise post-synthetic modification 45 of the phenyl rings of their structural components using various established organic reactions. Herein we demonstrate such a POP-based mercury 'nano-trap' that exhibits an exceptional mercury saturation uptake capacity of over 1,000 mg g À 1 and can effectively reduce Hg(II) concentration from 10 p.p.m.…”

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confidence: 99%

Mercury nano-trap for effective and efficient removal of mercury(II) from aqueous solution

et al. 2014

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Highly effective and highly efficient decontamination of mercury from aqueous media remains a serious task for public health and ecosystem protection. Here we report that this task can be addressed by creating a mercury 'nano-trap' as illustrated by functionalizing a high surface area and robust porous organic polymer with a high density of strong mercury chelating groups. The resultant porous organic polymer-based mercury 'nano-trap' exhibits a recordhigh saturation mercury uptake capacity of over 1,000 mg g À 1 , and can effectively reduce the mercury(II) concentration from 10 p.p.m. to the extremely low level of smaller than 0.4 p.p.b. well below the acceptable limits in drinking water standards (2 p.p.b.), and can also efficiently remove 499.9% mercury(II) within a few minutes. Our work therefore presents a new benchmark for mercury adsorbent materials and provides a new perspective for removing mercury(II) and also other heavy metal ions from contaminated water for environmental remediation.

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“…An alternative strategy for incorporating CUS into materials such as MOFs is then using organic linkers, for example metalated catechol groups. These types of groups have been successfully incorporated into porous materials using different synthesis strategies (Fei et al, 2014;Tanabe et al, 2010;Weston et al, 2012), and they have been studied theoretically as well (Colón et al, 2014;Getman et al, 2011;Raksakoon et al, 2015). Topology, linker length, and the number and position of metalated catechols in the linker all affect the spatial distribution and number density of CUS.…”

Section: Scenario 5: Methane Adsorption In Mof Systems With Localizedmentioning

confidence: 99%

Impact of the strength and spatial distribution of adsorption sites on methane deliverable capacity in nanoporous materials

Gómez-Gualdrón

Simon

Lassman

et al. 2017

Chemical Engineering Science

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Impact of the strength and spatial distribution of adsorption sites on methane deliverable capacity in nanoporous materials Chem Eng Sci 159, 18 (2017) ABSTRACT:The methane deliverable capacity of adsorbent materials is a critical performance metric that will determine the viability of using adsorbed natural gas (ANG) technology in vehicular applications. ARPA-E recently set a target deliverable capacity of 315 cc(STP)/cc that a viable adsorbent material should achieve to yield a driving range competitive with incumbent fuels.However, recent computational screening of hundreds of thousands of materials suggests that the target is unattainable. In this work, we aim to determine whether the observed limits in deliverable capacity (~200 cc(STP)/cc) are fundamental limits arising from thermodynamic or material design constraints. Our efforts focus on simulating methane adsorption isotherms in a large number of systems, resulting in a broad exploration of different combinations of spatial distributions and energetics of adsorption sites. All systems were classified into five adsorption scenarios with varying degrees of realism in the manner that adsorption sites are created and endowed with energetics. The scenarios range from methane adsorption on discrete idealized lattice sites to adsorption in metal-organic frameworks with coordinatively unsaturated sites (CUS) provided by metalated catechol groups. Our findings strongly suggest that the ARPA-E target is unattainable, although not due to thermodynamic constraints but due to material design constraints. On the other hand, we also find that the currently observed deliverable capacity limits may be moderately surpassed. For instance, incorporation of CUS in IRMOF-10 is predicted to yield a 217 cc(STP)/cc deliverable capacity. The modified material has a ~0.85 void fraction and a heat of adsorption of ~15 kJ/mol. This suggests that similar, moderate improvements over existing materials could be achieved as long as CUS incorporation still maintains a relatively large void fraction. Nonetheless, we conclude that more significant 3 improvements in deliverable capacity will require changes in the currently proposed operation conditions.

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Synthesis and Metalation of Catechol-Functionalized Porous Organic Polymers

Cited by 99 publications

References 34 publications

An assessment of strategies for the development of solid-state adsorbents for vehicular hydrogen storage

An assessment of strategies for the development of solid-state adsorbents for vehicular hydrogen storage

Mercury nano-trap for effective and efficient removal of mercury(II) from aqueous solution

Impact of the strength and spatial distribution of adsorption sites on methane deliverable capacity in nanoporous materials

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