Hlavním tématem práce je udržitelná laserem asistovaná syntéza Pd-NiOz nanočástic, které jsou použity k modifikaci částečně re-dukovaného grafen oxidu, přičemž částice i dekorované nanostruktury představují potenciální katalyzátory. Generované palladium-niklové koloidy byly vyrobeny reakcí v plazmatu s nízkou energií a skládají se z nanočástic NiOz o velikosti 30-40 nm obklopených7 nm Pd nanočásticemi. Chemická povaha směsi těchto nanočástic byla řízena množstvím Pd soli obsažené v procesu laserové syntézy. Toto řízení vedlo k tvorbě nanomateriálů kombinujících vysokou magnetickou citlivost a silné katalytické účinky. Na základě mode-lové redukce 4-NP, jednoho z nejhorších světových polutantů, bylo možné zjistit, že zvyšující se množství Pd vede ke zvýšení katalytického účinku, přičemž frekvence reakčního obratu pro nejvyšší koncentraci Pd překračuje3181 h1, což dle literatury konkuruje nejúčinnějším katalyzátorům na bázi paladia a nosiče. Kromě toho vzorek složený z 8,35 % Pd a 91,65 % Ni vykazuje vynikající úroveň nanesených nanočástic na grafenový materiál, což může přinést mnoho výhod v možných aplikacích v katalýze díky očekávanému navýšení katalytického účinku vyvolaného synergií mezi nanoslitinou a částečně redukovaným grafenem oxidu. Celkově tato práce představuje krok vpřed v jemné kontrole fyzikálně-chemických vlastností nanomateriálů, což má v konečném důsledku příznivý dopad na tak zásadní technologickou oblast, jakou je katalýza.
Anotace v angličtině
The central theme of the thesis is the eco-friendly laser-assisted synthesis of Pd-NiOz nanoparticles (NPs) decorating partly reduced graphene oxide (prGO) support for their use as catalysts. The NPs obtained in a colloidal form were produced from a low energy plasma reaction and consist of 30-40 nm size NiOz NPs surrounded by 7 nm Pd NPs. The chemical nature of these NPs mixture was controlled by the amount of Pd salt included in the laser-mediated synthesis process. Such control resulted in the design of nanomaterials combining high magnetic responsiveness and robust catalytic behaviour. As experimentally identified through the model reduction of 4-NP, one of the worst world pollutants, the increasing amount of Pd leads to increased catalytic performance. At the same time, the turnover frequency for the highest Pd concentration overcomes 3181 h1, which is competitive with the highest values of Pd NPs/support catalysts found in the literature. In addition, the sample composed of 8.35 wt% Pd and 91.65 wt% Ni exhibits an excellent decoration of prGO, which can bring many benefits for future applications in the catalysis field due to the expected catalytic enhancement prompted by the synergies between the nanoalloy and prGO. Overall, the current thesis represents a step forward in the fine control over the nanomaterials physicochemical features, which ultimately has a beneficial impact on a technological field as critical as catalysis.
reactive laser ablation, control of chemical composition, palladium nanoparticle, nickel nanoparticle, metal-support interaction, nanocatalyst, graphene-based nanosupport
Rozsah průvodní práce
107 s.
Jazyk
CZ
Anotace
Hlavním tématem práce je udržitelná laserem asistovaná syntéza Pd-NiOz nanočástic, které jsou použity k modifikaci částečně re-dukovaného grafen oxidu, přičemž částice i dekorované nanostruktury představují potenciální katalyzátory. Generované palladium-niklové koloidy byly vyrobeny reakcí v plazmatu s nízkou energií a skládají se z nanočástic NiOz o velikosti 30-40 nm obklopených7 nm Pd nanočásticemi. Chemická povaha směsi těchto nanočástic byla řízena množstvím Pd soli obsažené v procesu laserové syntézy. Toto řízení vedlo k tvorbě nanomateriálů kombinujících vysokou magnetickou citlivost a silné katalytické účinky. Na základě mode-lové redukce 4-NP, jednoho z nejhorších světových polutantů, bylo možné zjistit, že zvyšující se množství Pd vede ke zvýšení katalytického účinku, přičemž frekvence reakčního obratu pro nejvyšší koncentraci Pd překračuje3181 h1, což dle literatury konkuruje nejúčinnějším katalyzátorům na bázi paladia a nosiče. Kromě toho vzorek složený z 8,35 % Pd a 91,65 % Ni vykazuje vynikající úroveň nanesených nanočástic na grafenový materiál, což může přinést mnoho výhod v možných aplikacích v katalýze díky očekávanému navýšení katalytického účinku vyvolaného synergií mezi nanoslitinou a částečně redukovaným grafenem oxidu. Celkově tato práce představuje krok vpřed v jemné kontrole fyzikálně-chemických vlastností nanomateriálů, což má v konečném důsledku příznivý dopad na tak zásadní technologickou oblast, jakou je katalýza.
Anotace v angličtině
The central theme of the thesis is the eco-friendly laser-assisted synthesis of Pd-NiOz nanoparticles (NPs) decorating partly reduced graphene oxide (prGO) support for their use as catalysts. The NPs obtained in a colloidal form were produced from a low energy plasma reaction and consist of 30-40 nm size NiOz NPs surrounded by 7 nm Pd NPs. The chemical nature of these NPs mixture was controlled by the amount of Pd salt included in the laser-mediated synthesis process. Such control resulted in the design of nanomaterials combining high magnetic responsiveness and robust catalytic behaviour. As experimentally identified through the model reduction of 4-NP, one of the worst world pollutants, the increasing amount of Pd leads to increased catalytic performance. At the same time, the turnover frequency for the highest Pd concentration overcomes 3181 h1, which is competitive with the highest values of Pd NPs/support catalysts found in the literature. In addition, the sample composed of 8.35 wt% Pd and 91.65 wt% Ni exhibits an excellent decoration of prGO, which can bring many benefits for future applications in the catalysis field due to the expected catalytic enhancement prompted by the synergies between the nanoalloy and prGO. Overall, the current thesis represents a step forward in the fine control over the nanomaterials physicochemical features, which ultimately has a beneficial impact on a technological field as critical as catalysis.
reactive laser ablation, control of chemical composition, palladium nanoparticle, nickel nanoparticle, metal-support interaction, nanocatalyst, graphene-based nanosupport
Zásady pro vypracování
The general goal of the thesis is the synthesis of Ni-Pd nanoalloys for its possible exploitation in the catalysis field. The combination of laser ablation in liquids (LAL) and laser photoreduction/oxidation in liquids (LPL) will be employed to reach this aim.
Determine the aspects that enable the control over the elemental composition in the nanoalloys. This will be done by testing different laser parameters and the material's precursor concentrations.
Analyze different physicochemical properties in the recently created nanoalloys looking for outstanding characteristics derived from the combination of both materials.
Finally, the nanoalloys' catalytic behavior will be tested to degrade the organic pollutant 4-nitrophenol (4-NP), which transformation in 4- aminophenol (4-AP) is considered a model reaction for evaluating the catalytic activity of the newly developed catalyst. After evaluating the nanoalloys' catalytic capacities in the model reaction, we will test their utility in the fabrication of one of the most promising catalysts towards the reduction of organic pollutants; graphene oxide-based composites decorated with nanoparticles.
Zásady pro vypracování
The general goal of the thesis is the synthesis of Ni-Pd nanoalloys for its possible exploitation in the catalysis field. The combination of laser ablation in liquids (LAL) and laser photoreduction/oxidation in liquids (LPL) will be employed to reach this aim.
Determine the aspects that enable the control over the elemental composition in the nanoalloys. This will be done by testing different laser parameters and the material's precursor concentrations.
Analyze different physicochemical properties in the recently created nanoalloys looking for outstanding characteristics derived from the combination of both materials.
Finally, the nanoalloys' catalytic behavior will be tested to degrade the organic pollutant 4-nitrophenol (4-NP), which transformation in 4- aminophenol (4-AP) is considered a model reaction for evaluating the catalytic activity of the newly developed catalyst. After evaluating the nanoalloys' catalytic capacities in the model reaction, we will test their utility in the fabrication of one of the most promising catalysts towards the reduction of organic pollutants; graphene oxide-based composites decorated with nanoparticles.
Seznam doporučené literatury
[1] FERRANDO, Riccardo; JELLINEK, Julius; JOHNSTON, Roy L. Nanoalloys: from theory to applications of alloy clusters and nanoparticles. Chemical reviews, 2008, 108.3: 845-910. [2] AGUILERA-GRANJA, F., et al. Structural and magnetic properties of X 12 Y (X, Y= Fe, Co, Ni, Ru, Rh, Pd, and Pt) nanoalloys. The Journal of Chemical Physics, 2010, 132.18: 184507. [3] GAWANDE, Manoj B.; FORNASIERO, Paolo; ZBOŘIL, Radek. Carbon-Based Single-Atom Catalysts for Advanced Applications. ACS Catalysis, 2020, 10.3: 2231-2259. [4] GUISBIERS, G., et al. Size and shape effects on the phase diagrams of nickel-based bimetallic nanoalloys. The Journal of Physical Chemistry C, 2017, 121.12: 6930-6939. [5] ABDELSAYED, Victor, et al. Laser synthesis of bimetallic nanoalloys in the vapor and liquid phases and the magnetic properties of PdM and PtM nanoparticles (M= Fe, Co and Ni). Faraday Discussions, 2008, 138: 163-180. [6] ZHANG, Dongshi; GÖKCE, Bilal; BARCIKOWSKI, Stephan. Laser synthesis and processing of colloids: fundamentals and applications. Chemical reviews, 2017, 117.5: 3990-4103. [7] SAKAMOTO, Masanori; FUJISTUKA, Mamoru; MAJIMA, Tetsuro. Light as a construction tool of metal nanoparticles: Synthesis and mechanism. Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 2009, 10.1: 33-56. [8] MATSUMOTO, Ayumu, et al. Transfer of the species dissolved in a liquid into laser ablation plasma: an approach using emission spectroscopy. The Journal of Physical Chemistry C, 2015, 119.47: 26506-26511. [9] TORRES-MENDIETA, Rafael, et al. Laser-assisted synthesis of Fe-Cu oxide nanocrystals. Applied Surface Science, 2019, 469: 1007-1015. [10] SARAEVA, Irina Nikolaevna, et al. Laser synthesis of colloidal Si@ Au and Si@ Ag nanoparticles in water via plasma-assisted reduction. Journal of Photochemistry and Photobiology A: Chemistry, 2018, 360: 125-131. [11] REVATHY, T. A., et al. Highly active graphene-supported palladium-nickel alloy nanoparticles for catalytic reduction of 4-nitrophenol. Applied Surface Science, 2018, 449: 764-771. [12] GAO, Xiang, et al. Facile synthesis of PdNiP/Reduced graphene oxide nanocomposites for catalytic reduction of 4-nitrophenol. Materials Chemistry and Physics, 2019, 222: 391-397. [13] LEPPERT, Linn; KEMPE, Rhett; KÜMMEL, Stephan. Hydrogen binding energies and electronic structure of Ni–Pd particles: a clue to their special catalytic properties. Physical Chemistry Chemical Physics, 2015, 17.39: 26140-26148.
Seznam doporučené literatury
[1] FERRANDO, Riccardo; JELLINEK, Julius; JOHNSTON, Roy L. Nanoalloys: from theory to applications of alloy clusters and nanoparticles. Chemical reviews, 2008, 108.3: 845-910. [2] AGUILERA-GRANJA, F., et al. Structural and magnetic properties of X 12 Y (X, Y= Fe, Co, Ni, Ru, Rh, Pd, and Pt) nanoalloys. The Journal of Chemical Physics, 2010, 132.18: 184507. [3] GAWANDE, Manoj B.; FORNASIERO, Paolo; ZBOŘIL, Radek. Carbon-Based Single-Atom Catalysts for Advanced Applications. ACS Catalysis, 2020, 10.3: 2231-2259. [4] GUISBIERS, G., et al. Size and shape effects on the phase diagrams of nickel-based bimetallic nanoalloys. The Journal of Physical Chemistry C, 2017, 121.12: 6930-6939. [5] ABDELSAYED, Victor, et al. Laser synthesis of bimetallic nanoalloys in the vapor and liquid phases and the magnetic properties of PdM and PtM nanoparticles (M= Fe, Co and Ni). Faraday Discussions, 2008, 138: 163-180. [6] ZHANG, Dongshi; GÖKCE, Bilal; BARCIKOWSKI, Stephan. Laser synthesis and processing of colloids: fundamentals and applications. Chemical reviews, 2017, 117.5: 3990-4103. [7] SAKAMOTO, Masanori; FUJISTUKA, Mamoru; MAJIMA, Tetsuro. Light as a construction tool of metal nanoparticles: Synthesis and mechanism. Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 2009, 10.1: 33-56. [8] MATSUMOTO, Ayumu, et al. Transfer of the species dissolved in a liquid into laser ablation plasma: an approach using emission spectroscopy. The Journal of Physical Chemistry C, 2015, 119.47: 26506-26511. [9] TORRES-MENDIETA, Rafael, et al. Laser-assisted synthesis of Fe-Cu oxide nanocrystals. Applied Surface Science, 2019, 469: 1007-1015. [10] SARAEVA, Irina Nikolaevna, et al. Laser synthesis of colloidal Si@ Au and Si@ Ag nanoparticles in water via plasma-assisted reduction. Journal of Photochemistry and Photobiology A: Chemistry, 2018, 360: 125-131. [11] REVATHY, T. A., et al. Highly active graphene-supported palladium-nickel alloy nanoparticles for catalytic reduction of 4-nitrophenol. Applied Surface Science, 2018, 449: 764-771. [12] GAO, Xiang, et al. Facile synthesis of PdNiP/Reduced graphene oxide nanocomposites for catalytic reduction of 4-nitrophenol. Materials Chemistry and Physics, 2019, 222: 391-397. [13] LEPPERT, Linn; KEMPE, Rhett; KÜMMEL, Stephan. Hydrogen binding energies and electronic structure of Ni–Pd particles: a clue to their special catalytic properties. Physical Chemistry Chemical Physics, 2015, 17.39: 26140-26148.
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