Lock and key-based nanozyme model to understand the substituent effect on the hydrolysis of organophosphate-based nerve agents by Zr-incorporated cerium oxide

Khulbe, Kritika; Mugesh, Govindasamy

doi:10.1016/j.poly.2019.05.001

Cited by 11 publications

(6 citation statements)

References 48 publications

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“…15 In another study by Leonard et al, 16 a Ce-doped titania composite was used for detoxification of DMNP and showed 50% improved response compared to the bare titania. In addition, Khulbe and Mugesh 17 modified the surface of CeO 2 by introducing the Zr atoms within the lattice of CeO 2 to increase its performance toward degradation of DMNP to dimethyl phosphate (DMP). Despite the effectiveness of CeO 2 and ZrO 2 as potential catalysts for the detoxification of CWAs, their metal hydroxide counterparts are better candidates in the hydrolysis of organophosphorus compounds due to their higher degree of hydrophilicity.…”

Section: Introductionmentioning

confidence: 99%

Assessing Detoxification Performance of Metal Hydroxide@Polymer Composites Prepared via Matrix-Incorporation and Spray-Coating Techniques

Aina,

Mondal,

Rownaghi

et al. 2024

ACS Appl. Eng. Mater.

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Polymer-based composites with tunable physiochemical properties are great candidates for efficient destruction of toxic chemicals and vapors. Herein, we report the development of metal hydoxide@polymer composites via matrix-incorporation and spray-coating methods and the assessment of the impact of different preparation methods on their physiochemical properties and detoxification performance. Specifically, Zr(OH) 4 and Ce(OH) 4 were used to enhance the catalytic activity of Ultem, Matrimid, and PIM-1 polymers toward hydrolysis of dimethyl 4-nitrophenylphosphonate (DMNP) simulant. Two different preparation techniques were employed to assess the structure-performance relations in the developed composites in terms of DMNP detoxification performance. The results obtained indicated that surface-coated metal hydoxide@polymer composites outperformed their respective incorporated analogues for both Zr(OH) 4 and Ce(OH) 4 due to the presence of more accessible surface active sites. Moreover, it was found that Ce(OH) 4 gave rise to a faster detoxification rate than Zr(OH) 4 in both matrix-incorporated and surfacecoated composites owing to higher Lewis acidity of Ce(OH) 4 than Zr(OH) 4 . Among the materials investigated, the best-performing material was found to be surface-coated Ce(OH) 4 @PIM-1, which exhibited the fastest DMNP detoxification rate of 0.08 min −1 and the shortest half-life of 8.67 min. The findings of this investigation highlight the potential of the spray-coating method for fabricating composites effective for detoxification of toxic chemicals and vapors.

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Section: Introductionmentioning

confidence: 99%

Assessing Detoxification Performance of Metal Hydroxide@Polymer Composites Prepared via Matrix-Incorporation and Spray-Coating Techniques

Aina,

Mondal,

Rownaghi

et al. 2024

ACS Appl. Eng. Mater.

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“…Ceria can exist in dual oxidation states as Ce 3+ and Ce 4+ , enabling the ability to accommodate a high density of oxygen vacancies (Vo), which enhances the catalytic activity for OPD due to the cooperative redox property of Ce 3+ and Ce 4+ [1,6,9,11] . The addition of metal dopants to ceria has shown to improve Vo concentration and associated catalytic activity for the decomposition of OPs [1,12–15] …”

Section: Introductionmentioning

confidence: 99%

“…[1,6,9,11] The addition of metal dopants to ceria has shown to improve Vo concentration and associated catalytic activity for the decomposition of OPs. [1,[12][13][14][15] Various approaches can be applied to synthesize oxide nanocatalysts to tune structure and thus catalytic properties; however, the majority of preparation methods exhibit common drawbacks, such as complicated synthetic procedures and/or energy intensive processes. [6,[16][17][18][19] To alleviate these concerns, benign biomineralization-based methods have received increased attention as a straightforward and efficient synthesis approach for metal oxide catalysts.…”

Section: Introductionmentioning

confidence: 99%

Modulating Ce³⁺ Sites in Ce‐Zr Oxide Nanocatalysts through Protamine Biomineralization for Organophosphate Dephosphorylation

Jiang,

Peña,

Hadinata Lie

et al. 2024

ChemCatChem

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Catalytic is a crucial reaction for environmental detoxication of pesticides and neutralization of various molecules classified as chemical warfare agents. Herein, we report on a series of tunable Ce‐Zr‐based metal oxides, (ZraCe1‐aOx) prepared using a facile biomineralization technique, as catalysts for organophosphates dephosphorylation. Synchrotron scattering and spectroscopy methods showcase that ZraCe1‐aOx catalysts are highly defective and exhibit an abundance of Ce3+ sites that promote oxygen vacancies needed for enhanced dephosphorylation reactions. The catalytic performance was assessed using a model para‐nitrophenyl phosphate reaction and showcases a strong dependence on Zr dopant concentration and subsequent tuning of the Ce3+/Ce4+ ratio. Analysis of synchrotron datasets allowed structure‐performance correlations between the Ce3+ concentration and associated oxygen vacancies, the dephosphorylation rate constant, and Zr concentration to be established, confirming that Ce3+ as active sites is positively correlated with the rate constant. We envision that similar biomineralization approaches can be used to fabricate Ce3+‐rich Ce‐Zr oxide for environmental application in dephosphorylation and other hydrolysis reactions.

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“…pathway while later Kuchma et al [6] foundt he activity is proportional to the concentration of surface Ce 3+ .Abalanced surface Ce 4+ /Ce 3+ ratio [7] and surface oxygen vacancy [8] were also proposed the key factor facilitating this CeO 2 -catalyzed dephosphorylation. Although aw ide range of Ce-based catalysts have been reported to catalyze this reaction, [9][10][11][12] the key surface Ce species and the underlying mechanism are still unclear. Using probe-assisted nuclear magnetic resonance (NMR), we recently demonstrated that the electronic state (i.e., Lewis acidity) of surface Ce shifts "continuously" with its local structure and cannot be ascribed to the "discrete" oxidation state (e.g., 3+ and 4 + for Ce) as in literatures above.…”

Section: Introductionmentioning

confidence: 99%

Electronic‐State Manipulation of Surface Titanium Activates Dephosphorylation Over TiO₂ Near Room Temperature

Wang

Chen

et al. 2021

Angew Chem Int Ed

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Dephosphorylation that removes a phosphate group from substrates is an important reaction for living organisms and environmental protection. Although CeO2 has been shown to catalyze this reaction, cerium is low in natural abundance and has a narrow global distribution (>90 % of these reserves are located within six countries). It is thus imperative to find another element/material with high worldwide abundance that can also efficiently extract the phosphate out of agricultural waste for phosphorus recycle. Using para‐nitrophenyl phosphate (p‐NPP) as a model compound, we demonstrate that TiO2 with a F‐modified (001) surface can activate p‐NPP dephosphorylation at temperatures as low as 40 °C. By probe‐assisted nuclear magnetic resonance (NMR), it was revealed that the strong electron‐withdrawing effect of fluorine makes Ti atoms (the active sites) on the (001) surface very acidic. The bidentate adsorption of p‐NPP on this surface further promotes its subsequent activation with a barrier ≈20 kJ mol−1 lower than that of the pristine (001) and (101) surfaces, allowing the activation of this reaction near room temperature (from >80 °C).

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Lock and key-based nanozyme model to understand the substituent effect on the hydrolysis of organophosphate-based nerve agents by Zr-incorporated cerium oxide

Cited by 11 publications

References 48 publications

Assessing Detoxification Performance of Metal Hydroxide@Polymer Composites Prepared via Matrix-Incorporation and Spray-Coating Techniques

Assessing Detoxification Performance of Metal Hydroxide@Polymer Composites Prepared via Matrix-Incorporation and Spray-Coating Techniques

Modulating Ce³⁺ Sites in Ce‐Zr Oxide Nanocatalysts through Protamine Biomineralization for Organophosphate Dephosphorylation

Electronic‐State Manipulation of Surface Titanium Activates Dephosphorylation Over TiO₂ Near Room Temperature

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Lock and key-based nanozyme model to understand the substituent effect on the hydrolysis of organophosphate-based nerve agents by Zr-incorporated cerium oxide

Cited by 11 publications

References 48 publications

Assessing Detoxification Performance of Metal Hydroxide@Polymer Composites Prepared via Matrix-Incorporation and Spray-Coating Techniques

Assessing Detoxification Performance of Metal Hydroxide@Polymer Composites Prepared via Matrix-Incorporation and Spray-Coating Techniques

Modulating Ce3+ Sites in Ce‐Zr Oxide Nanocatalysts through Protamine Biomineralization for Organophosphate Dephosphorylation

Electronic‐State Manipulation of Surface Titanium Activates Dephosphorylation Over TiO2 Near Room Temperature

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Product

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Modulating Ce³⁺ Sites in Ce‐Zr Oxide Nanocatalysts through Protamine Biomineralization for Organophosphate Dephosphorylation

Electronic‐State Manipulation of Surface Titanium Activates Dephosphorylation Over TiO₂ Near Room Temperature