Enhanced activity for the oxygen reduction reaction in microporous water

Thorarinsdottir, Agnes E.; Erdosy, Daniel P.; Costentin, Cyrille; Mason, Jarad A.; Nocera, Daniel G.

doi:10.1038/s41929-023-00958-9

Cited by 34 publications

(20 citation statements)

References 46 publications

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“…10 A local environment for the catalysts offering suitable hydrophobicity could reduce water adsorption and promote diffusion and affinity of the reagent to the electrode interface. 3,11 Creating a hydrophobic microenvironment for heterogeneous catalysis usually relies on external hydrophobic coatings, 12,13 making it challenging to control the local concentrations of reagents. Electro-driven hydrophobicity switches provide a reversible alternative that proved to be effective for catalysts with metal oxides and conjugate polymers.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Porous materials with hydrophobic internal and hydrophilic external surfaces could potentially balance the physisorptive interactions between water and the reagent substrates, leading to fast exchange kinetics well suited for liquid-phase electrochemical catalysis. 3 Electrochemical ammonia (NH 3 ) synthesis by NO 3 − reduction has developed as a facile alternative to nitrogen reduction due to the relatively low dissociation energy of the N�O bonds and their rich abundance in nature, particularly in current environmental pollutants. 4,9,20−24 However, for electrocatalytic NO 3 − reduction to NH 3 , the proton-coupled eight-electron transfer process requires more negative applied potential relative to proton reduction and a higher proton concentration relative to the two-electron reduction to nitrite (NO 2 − ).…”

Section: ■ Introductionmentioning

confidence: 99%

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Molecular Self-Assembly in Conductive Covalent Networks for Selective Nitrate Electroreduction to Ammonia

Sun,

Gao,

et al. 2023

J. Am. Chem. Soc.

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Electrochemical nitrate (NO3 –) reduction in aqueous media provides a useful approach for ammonia (NH3) synthesis. While efforts are focused on developing catalysts, the local microenvironment surrounding the catalyst centers is of great importance for controlling electrocatalytic performance. Here, we demonstrate that a self-assembled molecular iron catalyst integrated in a free-standing conductive hydrogel is capable of selective production of NH3 from NO3 – at efficiencies approaching unity. With the electrocatalytic hydrogel, the NH3 selectivity is consistently high under a range of negative biases, which results from the hydrophobicity increase of the polycarbazole-based electrode substrate. In mildly acidic media, proton reduction is suppressed by electro-dewetting of the hydrogel electrode, enhancing the selectivity of NO3 – reduction. The electrocatalytic hydrogel is capable of continuous production of NH3 for at least 100 h with NH3 selectivity of ∼89 to 98% at high current densities. Our results highlight the role of constructing an internal hydrophobic surface for electrocatalysts in controlling selectivity in aqueous media.

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Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Molecular Self-Assembly in Conductive Covalent Networks for Selective Nitrate Electroreduction to Ammonia

Sun,

Gao,

et al. 2023

J. Am. Chem. Soc.

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“…The low solubility of gases in water is a critical challenge for many energy and biomedical technologies that require high concentrations of gas molecules to be rapidly transported through an aqueous environment. − Owing to their high internal surface areas, , microporous materialssuch as zeolites and metal–organic frameworkscan be used to dramatically enhance the gas density contained within an aqueous fluid, provided colloidally stable aqueous dispersions can be formed in which the micropores remain dry and accessible to gas molecules . Such dispersionstermed ″microporous water″are possible when microporous particles are constructed with external surfaces that are sufficiently hydrophilic to promote dispersibility in water and internal surfaces that are sufficiently hydrophobic to make it thermodynamically unfavorable for liquid water to intrude into the pores.…”

Section: Introductionmentioning

confidence: 99%

Design Principles for Using Amphiphilic Polymers To Create Microporous Water

DelRe,

Hong,

Wenny

et al. 2023

J. Am. Chem. Soc.

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Aqueous dispersions of microporous nanocrystals with dry, gas-accessible pores�referred to as "microporous water"�enable high densities of gas molecules to be transported through water. For many applications of microporous water, generalizable strategies are required to functionalize the external surface of microporous particles to control their dispersibility, stability, and interactions with other solution-phase components� including catalysts, proteins, and cells�while retaining as much of their internal pore volume as possible. Here, we establish design principles for the noncovalent surface functionalization of hydrophobic metal−organic frameworks with amphiphilic polymers that render the particles dispersible in water and enhance their hydrolytic stability. Specifically, we show that block co-polymers with persistence lengths that exceed the micropore aperture size of zeolitic imidazolate frameworks (ZIFs) can dramatically enhance ZIF particle dispersibility and stability while preserving porosity and >80% of the theoretical O 2 carrying capacity. Moreover, enhancements in hydrolytic stability are greatest when the polymer can form strong bonds to exposed metal sites on the external particle surface. More broadly, our insights provide guidelines for controlling the interface between polymers and metal−organic framework particles in aqueous environments to augment the properties of microporous water.

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“…4−7 As shown in Figure 1, research progress has successively witnessed achievements in both synthesis protocols and application extensions although the period of development is relatively short, especially the past four years that have demonstrated that the "dam" for PLs has burst. 8 Additionally, the establishment of the company "Porous Liquid Technologies" unquestionably accelerates the pace of commercialization toward practical applications.…”

Section: Introductionmentioning

confidence: 99%

“…Additionally, the flowing ability of PLs provides enormous convenience for the industrial pumping process . Thus, PLs have shown enormous potential in a plethora of applications ranging from gas selective sorption, membrane separation, homogeneous catalysis, chiral separation to biomedical science, etc. − As shown in Figure , research progress has successively witnessed achievements in both synthesis protocols and application extensions although the period of development is relatively short, especially the past four years that have demonstrated that the “dam” for PLs has burst . Additionally, the establishment of the company “Porous Liquid Technologies” unquestionably accelerates the pace of commercialization toward practical applications.…”

Section: Introductionmentioning

confidence: 99%

Porous Liquids Open New Horizons: Synthesis, Applications, and Prospects

Wang,

Ying,

Xin

et al. 2023

Acc. Mater. Res.

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Conspectus Though the idea of liquids with accessible porosity seems counterintuitive, porous liquids (PLs) have indeed demonstrated themselves to hold great promise in versatile fields, thus arousing great attention and interests from both academic and industrial communities since the concept of PLs was first proposed in 2007. PLs are a novel class of a flowing liquid system that possesses accessible permanent porosity, and they integrate the processable advantages of liquids with superior accommodative capacities of porous solids. By and large, the development of PLs went through the starting stage of the concept proposal and the arrival stage of various synthesized examples to the period of application-specific extensions. From the point of view of producing functions, PLs consist of two parts: sterically hindered solvents and pore generators. Correspondingly, pore generators provide accessible cavities for the resultant PLs, while sterically hindered solvents endow pore generators with a flowing behavior. Undoubtedly, engineering permanent porosity with shape-persistent cavities into a liquid is leading to an inherent change that porosity can not only be created in conventional solids, thus providing new opportunities by utilizing the processability of PLs. Therefore, the field of PLs has seen considerable progress in the design, synthesis, and emerging applications since the example of hollow silica based PLs was demonstrated by Dai et al. in 2015 (Porous Liquids: A Promising Class of Media for Gas Separation.Angew. Chem., Int. Ed. Engl.201554932936), especially during the past four years. Until now, PLs have emerged as promising platforms for a variety of applications, including but not limited to gas capture, molecule separation, catalytic conversion, biomedicine, and beyond. Anyhow, the further development toward practical applications of PLs depends heavily on the universal synthesis method and the process optimization, where the former is undoubtedly the core. This Account mainly showcases the evolution of our recent progress in the design and synthesis of PLs. Importantly, we tell the story of how we apply the synthesis idea of another similar liquidlike material (i.e., solvent-free nanofluids, SFNs) that has been investigated for more than 20 years in our laboratory in the preparation of PLs. Emphasis is put on the construction of PLs from the perspective of interface interactions (e.g., the electrostatic interaction, the acid–base interaction, and the dipole–dipole/quadrupole interaction, etc.) between sterically hindered solvents and pore generators. Then, we present and summarize related applications in the field of environmental remediation including gas sorption, membrane separation, metal ion selective sorption, and extractive desulfurization, etc. Finally, the challenges, opportunities, and future directions in developing novel PLs are provided and outlined. It is expected that this Account will stimulate the interest of researchers working in broadly diverse fields to fully unleash the potent...

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Enhanced activity for the oxygen reduction reaction in microporous water

Cited by 34 publications

References 46 publications

Molecular Self-Assembly in Conductive Covalent Networks for Selective Nitrate Electroreduction to Ammonia

Molecular Self-Assembly in Conductive Covalent Networks for Selective Nitrate Electroreduction to Ammonia

Design Principles for Using Amphiphilic Polymers To Create Microporous Water

Porous Liquids Open New Horizons: Synthesis, Applications, and Prospects

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