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Interface Engineering of MoS2/Ni3S2 Heterostructures for Highly Enhanced Electrochemical Overall Water Splitting ActivityZhang, Jian, Wang, Tao, Pohl, Darius, Rellinghaus, Bernd, Dong, Renhao, Liu, Shaohua, Zhuang, Xiaodong, Feng, Xinliang 08 May 2018 (has links) (PDF)
To achieve sustainable production of H2 fuel through water splitting, low-cost electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are required to replace Pt and IrO2 catalysts. Here, for the first time, we present the interface engineering of novel MoS2/Ni3S2 heterostructures, in which abundant interfaces are formed. For OER, such MoS2/Ni3S2 heterostructures show an extremely low overpotential of ~218 mV at 10 mA cm-2, which is superior to that of the state-of-the-art OER electrocatalysts. Using MoS2/Ni3S2 heterostructures as bifunctional electrocatalysts, an alkali electrolyser delivers a current density of 10 mA cm-2 at a very low cell voltage of ~1.56 V. In combination with density function theory (DFT) calculations, this study demonstrates that the constructed interfaces synergistically favor the chemisorption of hydrogen and oxygencontaining intermediates, thus accelerating the overall electrochemical water splitting.
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Photosynthetische Wasseroxidation: Über Liganden und Zwischenprodukte / Photosynthetic Water Oxidation:Ligands and IntermediatesClausen, Jürgen 20 August 2004 (has links)
Photosynthetic water oxidation to yield the oxygen of the atmosphere is of paramount biological and also technical relevance, in the light of decreasing fossil fuel reserves. The splitting of water into hydrogen (on carriers) and oxygen takes place in a multimeric protein called Photosystem II (PSII). The rigorous understanding of nature´s solution for this thermodynamically and mechanistically highly demanding reaction is one approach towards the construction of an artificial hydrogen technology under exploitation of almost unlimited energy sources, sunlight and an ubiquitous substrate, water. This thesis aims at two aspects: (i) Electron and proton transferring amino acids and (ii) so far undetected chemical intermediates between water and O2(i) D1-Glu189 has been claimed to be involved (a) in the proton conducting network around the Mn4Ca-cluster and (b) as a direct ligand to Mn. We exchanged the negative Glu against the positive Arg or Lys or the neutral Glu without any effect on the relaxation times (ns-ms) of the various electron transfers in PSII. Our data exclude these postulated roles of D1-Glu189 and qualify a recently published structural model.(ii) Dioxygen is produced in what seems to be a single reaction step, although it involves the transfer of four electrons from bound water to the fourfold oxidised catalytic centre. No chemical intermediate (e.g. peroxide) has been detected by high resolving optical and magnetical spectroscopy. To overcome the detection problem of short lived intermediates we pushed the process backward by elevated oxygen pressure and found the first evidence for such an intermediate. The astonishing half suppression of oxygen evolution at only 2.3 bar O2 emphasised the small driving force of this important reaction. PSII operates at the energetic limits; this is why the atmospheric oxygen level cannot be pushed much above the present level.
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Untersuchungen zur Dissoziation von Wasser durch Einwirkung hochfrequenter elektromagnetischer FelderSchneider, Jens 12 November 2012 (has links) (PDF)
Während die Wasserdissoziation mit der Hilfe von Gleichstrom (Wasser-Elektrolyse) einen gut untersuchten Prozess darstellt, war der Mechanismus der Wasserdissoziation durch Einwirkung hochfrequenter (HF) elektromagnetischer Felder als relativ neues Phänomen noch nicht vollständig aufgeklärt.
Für die Realisierung der Wasserdissoziation in HF-Feldern mit einer Frequenz von 13,56 MHz wurde in dieser Arbeit ein neuartiger experimenteller Aufbau verwendet, dessen Kernstück aus einem sich zwischen zwei parallelen Elektroden befindlichen Glasreaktor, der über eine Durchmesserverjüngung verfügte, bestand. Dieser Aufbau ermöglichte die Untersuchung der wässrigen Elektrolytlösung in den drei Phasen Erwärmung, Blasenbildung und Entladung mit Gasbildung. Die messbare Gasbildungsrate wurde als ein Maß für die Intensität der Wasserdissoziation gewählt. Ihre Abhängigkeit von der HF-Spannung, der HF-Leistung, der Art des Elektrolyten, der Konzentration des Elektrolyten und dem geometrischen Aufbau des Reaktors wurden untersucht.
Bei vielen Elektrolyten bestand das produzierte Gas vollständig aus Wasserstoff und Sauerstoff im molaren Verhältnis von 2 zu 1 sowie aus Wasserdampf. Für einige Elektrolyte wurden davon abweichende Verhalten hinsichtlich der Stöchiometrie beobachtet.
Das im Zusammenhang mit der Wasserdissoziation emittierte Licht wurde spektroskopisch untersucht. Es konnten angeregte OH-, H- und O-Radikale nachgewiesen werden. Dieser Befund legt nahe, dass die Wasserdissoziation durch die Wechselwirkung von hochenergetischen Elektronen mit Wassermolekülen verursacht wird. Der Versuchsaufbau ermöglichte also die Ausbildung eines nicht-thermischen Plasmas in der Gasphase im Bereich der Reaktorverjüngung.
Mit Hilfe von Simulationsrechnungen konnte der Verlauf des elektrischen Feldes in Abhängigkeit von der Elektrolytkonzentration für den gewählten Versuchsaufbau modelliert werden. Das Erreichen der für die Initiierung von selbsterhaltenden Entladungen in Wasserdampf notwendigen Feldstärke von 2,6 MV/m wurde durch die Modellierung verifiziert. Modellrechnungen stehen im Einklang mit dem vorgeschlagenen Mechanismus der HF-Wasserdissoziation.
Des Weiteren wurde das Anwendungspotenzial der Radikalbildung für den Abbau von Modellschadstoffen wie Perfluoroktansäure (PFOA) untersucht. Der Abbau perfluorierter Verbindungen, der bisher durch eine wenig effiziente thermische Totaloxidation erreicht werden kann, konnte mit dem Plasmaprozess erfolgreich demonstriert werden.
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Theoretical description of water splitting on TiO2 and combined Mo2C-graphene based materialsRodríguez Hernández, Fermín 22 August 2017 (has links) (PDF)
The electrocatalytic water decomposition has been investigated in this thesis by means of its two half standard reactions: the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER). These reactions occur in different locations in a typical electrochemical cell: the anode and the cathode, respectively. Motivated by the lack of understanding about the reaction mechanisms occurring at the anodes and cathodes, we have proposed first: novel representations of typical TiO2 surfaces, based on small cluster systems, which can be used for a quick and more detailed assessment of the OER activities at modified TiO2 surfaces, and secondly we investigated the HER in two sets of model surfaces which represent recently synthesized materials, based on Mo2C and graphene with promising activities toward the HER. We have employed Density Functional Theory (DFT) based methods within both localized and extended basis sets, as implemented in GAMESS and VASP packages, respectively, to examine the structural, electronic and vibrational properties of the proposed models.
We propose new reaction mechanisms for the OER on a number of molecular representations of TiO2 electrodes. For each reaction pathway, the free energy profile is computed, at different biases, from the DFT energies, the entropic and the zero-point energy contributions. The mechanisms explored in this thesis are found to be energetically more feasible than alternative reaction pathways considered in previous theoretical works based on molecular representations of the TiO2 surfaces. The representation of the surface of specific, commonly occurring, titanium dioxide crystals (e.g., rutile and anatase) within the small cluster approximation is able to reproduce qualitatively the rutile (110) outperforming of the anatase (001) surface.
We subsequently investigate the influence of doping TiO2 surfaces with transition metals (TMs) on the performance of TiO2 -based electrodes for the water splitting electrochemical reaction. Two cluster models of the TM-doped active sites which resemble both the TiO2 anatase (001) and rutile (110) surfaces, respectively, are considered for the evaluation of the water decomposition reaction when a Ti is replaced by a TM atom. A set of TMs spanning from Vanadium to Nickel is considered. The late TMs explored here: Fe, Co and Ni are found to reproduce the observed experimental trends for the overpotentials in TiO2-doped electrodes. In the case of Cr and Mn, the present study predicts an enhancement of the OER activity for the anatase-like clusters while a reduction of this activity is found for the rutile-like ones. The vanadium-doped structures do not show relevant influence in the OER activity compared to pure TiO2-based cluster models.
The last part of this work is devoted to the theoretical study of the HER on recently found materials based on the synergistic combination of molybdenum carbide and graphene layers. We propose two major structural models to describe the HER mechanism within the framework of DFT: Mo2C-based clusters adsorbed on carbon nanosheets and the Mo2C (001) surface covered by pure and nitrogen-doped graphene layers. The former system evaluates the influence of Mo2C nanoparticles adsorbed on carbon nanosheets towards the HER. The second one is employed to gain insight about the high HER activity observed in molybdenum carbide anchored on nitrogen-doped porous carbon nanosheets (Mo2C@2D-NPC), recently synthesized. The H-adsorption free energy has been used as a principal descriptor to asses the HER activity at the proposed model active sites. It resembles the value for the best state of the art catalyst for the HER (i.e., platinum at carbon substrate Pt@C) in some of the proposed structural models. Furthermore, a pH-correction is added within a simplified model, to the H-adsorption free energy barrier in every proposed structure. The pH dependence of the H-adsorption free energy barriers allows the assessment of the HER at acidic and alkaline conditions simultaneously. An overall agreement with experimental results is found and further predictions, promoting the development of better HER catalysts, have been done.
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Theoretical description of water splitting on TiO2 and combined Mo2C-graphene based materialsRodríguez Hernández, Fermín 08 October 2017 (has links)
The electrocatalytic water decomposition has been investigated in this thesis by means of its two half standard reactions: the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER). These reactions occur in different locations in a typical electrochemical cell: the anode and the cathode, respectively. Motivated by the lack of understanding about the reaction mechanisms occurring at the anodes and cathodes, we have proposed first: novel representations of typical TiO2 surfaces, based on small cluster systems, which can be used for a quick and more detailed assessment of the OER activities at modified TiO2 surfaces, and secondly we investigated the HER in two sets of model surfaces which represent recently synthesized materials, based on Mo2C and graphene with promising activities toward the HER. We have employed Density Functional Theory (DFT) based methods within both localized and extended basis sets, as implemented in GAMESS and VASP packages, respectively, to examine the structural, electronic and vibrational properties of the proposed models.
We propose new reaction mechanisms for the OER on a number of molecular representations of TiO2 electrodes. For each reaction pathway, the free energy profile is computed, at different biases, from the DFT energies, the entropic and the zero-point energy contributions. The mechanisms explored in this thesis are found to be energetically more feasible than alternative reaction pathways considered in previous theoretical works based on molecular representations of the TiO2 surfaces. The representation of the surface of specific, commonly occurring, titanium dioxide crystals (e.g., rutile and anatase) within the small cluster approximation is able to reproduce qualitatively the rutile (110) outperforming of the anatase (001) surface.
We subsequently investigate the influence of doping TiO2 surfaces with transition metals (TMs) on the performance of TiO2 -based electrodes for the water splitting electrochemical reaction. Two cluster models of the TM-doped active sites which resemble both the TiO2 anatase (001) and rutile (110) surfaces, respectively, are considered for the evaluation of the water decomposition reaction when a Ti is replaced by a TM atom. A set of TMs spanning from Vanadium to Nickel is considered. The late TMs explored here: Fe, Co and Ni are found to reproduce the observed experimental trends for the overpotentials in TiO2-doped electrodes. In the case of Cr and Mn, the present study predicts an enhancement of the OER activity for the anatase-like clusters while a reduction of this activity is found for the rutile-like ones. The vanadium-doped structures do not show relevant influence in the OER activity compared to pure TiO2-based cluster models.
The last part of this work is devoted to the theoretical study of the HER on recently found materials based on the synergistic combination of molybdenum carbide and graphene layers. We propose two major structural models to describe the HER mechanism within the framework of DFT: Mo2C-based clusters adsorbed on carbon nanosheets and the Mo2C (001) surface covered by pure and nitrogen-doped graphene layers. The former system evaluates the influence of Mo2C nanoparticles adsorbed on carbon nanosheets towards the HER. The second one is employed to gain insight about the high HER activity observed in molybdenum carbide anchored on nitrogen-doped porous carbon nanosheets (Mo2C@2D-NPC), recently synthesized. The H-adsorption free energy has been used as a principal descriptor to asses the HER activity at the proposed model active sites. It resembles the value for the best state of the art catalyst for the HER (i.e., platinum at carbon substrate Pt@C) in some of the proposed structural models. Furthermore, a pH-correction is added within a simplified model, to the H-adsorption free energy barrier in every proposed structure. The pH dependence of the H-adsorption free energy barriers allows the assessment of the HER at acidic and alkaline conditions simultaneously. An overall agreement with experimental results is found and further predictions, promoting the development of better HER catalysts, have been done.
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Interface Engineering of MoS2/Ni3S2 Heterostructures for Highly Enhanced Electrochemical Overall Water Splitting Activity: Interface Engineering of MoS2/Ni3S2 Heterostructures for Highly Enhanced Electrochemical Overall Water Splitting ActivityZhang, Jian, Wang, Tao, Pohl, Darius, Rellinghaus, Bernd, Dong, Renhao, Liu, Shaohua, Zhuang, Xiaodong, Feng, Xinliang 08 May 2018 (has links)
To achieve sustainable production of H2 fuel through water splitting, low-cost electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are required to replace Pt and IrO2 catalysts. Here, for the first time, we present the interface engineering of novel MoS2/Ni3S2 heterostructures, in which abundant interfaces are formed. For OER, such MoS2/Ni3S2 heterostructures show an extremely low overpotential of ~218 mV at 10 mA cm-2, which is superior to that of the state-of-the-art OER electrocatalysts. Using MoS2/Ni3S2 heterostructures as bifunctional electrocatalysts, an alkali electrolyser delivers a current density of 10 mA cm-2 at a very low cell voltage of ~1.56 V. In combination with density function theory (DFT) calculations, this study demonstrates that the constructed interfaces synergistically favor the chemisorption of hydrogen and oxygencontaining intermediates, thus accelerating the overall electrochemical water splitting.
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Untersuchungen zur Dissoziation von Wasser durch Einwirkung hochfrequenter elektromagnetischer FelderSchneider, Jens 16 October 2012 (has links)
Während die Wasserdissoziation mit der Hilfe von Gleichstrom (Wasser-Elektrolyse) einen gut untersuchten Prozess darstellt, war der Mechanismus der Wasserdissoziation durch Einwirkung hochfrequenter (HF) elektromagnetischer Felder als relativ neues Phänomen noch nicht vollständig aufgeklärt.
Für die Realisierung der Wasserdissoziation in HF-Feldern mit einer Frequenz von 13,56 MHz wurde in dieser Arbeit ein neuartiger experimenteller Aufbau verwendet, dessen Kernstück aus einem sich zwischen zwei parallelen Elektroden befindlichen Glasreaktor, der über eine Durchmesserverjüngung verfügte, bestand. Dieser Aufbau ermöglichte die Untersuchung der wässrigen Elektrolytlösung in den drei Phasen Erwärmung, Blasenbildung und Entladung mit Gasbildung. Die messbare Gasbildungsrate wurde als ein Maß für die Intensität der Wasserdissoziation gewählt. Ihre Abhängigkeit von der HF-Spannung, der HF-Leistung, der Art des Elektrolyten, der Konzentration des Elektrolyten und dem geometrischen Aufbau des Reaktors wurden untersucht.
Bei vielen Elektrolyten bestand das produzierte Gas vollständig aus Wasserstoff und Sauerstoff im molaren Verhältnis von 2 zu 1 sowie aus Wasserdampf. Für einige Elektrolyte wurden davon abweichende Verhalten hinsichtlich der Stöchiometrie beobachtet.
Das im Zusammenhang mit der Wasserdissoziation emittierte Licht wurde spektroskopisch untersucht. Es konnten angeregte OH-, H- und O-Radikale nachgewiesen werden. Dieser Befund legt nahe, dass die Wasserdissoziation durch die Wechselwirkung von hochenergetischen Elektronen mit Wassermolekülen verursacht wird. Der Versuchsaufbau ermöglichte also die Ausbildung eines nicht-thermischen Plasmas in der Gasphase im Bereich der Reaktorverjüngung.
Mit Hilfe von Simulationsrechnungen konnte der Verlauf des elektrischen Feldes in Abhängigkeit von der Elektrolytkonzentration für den gewählten Versuchsaufbau modelliert werden. Das Erreichen der für die Initiierung von selbsterhaltenden Entladungen in Wasserdampf notwendigen Feldstärke von 2,6 MV/m wurde durch die Modellierung verifiziert. Modellrechnungen stehen im Einklang mit dem vorgeschlagenen Mechanismus der HF-Wasserdissoziation.
Des Weiteren wurde das Anwendungspotenzial der Radikalbildung für den Abbau von Modellschadstoffen wie Perfluoroktansäure (PFOA) untersucht. Der Abbau perfluorierter Verbindungen, der bisher durch eine wenig effiziente thermische Totaloxidation erreicht werden kann, konnte mit dem Plasmaprozess erfolgreich demonstriert werden.
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Transition-metal-based composite and hybrid nanomaterials for catalytic applicationsZhang, Rui 12 June 2018 (has links)
In der Entwicklung von Technologien für die nachhaltige Erzeugung, Speicherung und Umwandlung von Energie werden Hochleistungskatalysatoren benötigt. Im Rahmen dieser Arbeit werden verschiedene Übergangsmetall-basierte Katalysatoren, namentlich TiO2/Kohlenstoff-Komposite, anorganisch-organische Hybridsysteme auf Basis von NiFe Phosphonaten sowie Ni Phosphide, synthetisiert, charakterisiert und hinsichtlich ihrer photo- und elektrokatalytischen Eigenschaften untersucht.
Es wird gezeigt, dass die Grenzflächeneigenschaften der TiO2/C-Komposite signifikant durch die Gestaltung des Heizvorgangs während der Synthese beeinflusst werden. Insbesondere der Einsatz von Mikrowellenstrahlung vermag die Synthese von Kohlenstoff-basierten Materialien positiv zu beeinflussen. Schnelles Erwärmen führt zu stärkeren Wechselwirkungen zwischen Nanopartikeln und Kohlenstoff, einheitlicheren Beschichtungen und kleineren Partikeln mit schmaleren Partikelgrößenverteilungen, wodurch die photokatalytische Aktivität verbessert wird.
Schichtartige, hybride NiFe-Phenylphosphonat-Materialien werden ausgehend in Benzylalkohol dargestellt und ihre Aktivität in der OER im basischen Milieu untersucht. Die Hybridpartikel werden in-situ in NiFe-Hydroxid Nanoschichten umgewandelt. Röntgenspektroskopische Untersuchungen deuten auf eine induzierte, teilweise verzerrte Koordinationsumgebung der Metallzentren im Katalysator hin. Die Kombination der synergistischen Effekte zwischen Ni und Fe mit den strukturellen Eigenschaften des Hybridmaterials ermöglicht einen effizienten Katalysator.
Weiterhin werden Nickel-Phosphide durch die thermische Behandlung der Phenyl- oder Methylphosphonate des Nickels, welche Schichtstrukturen aufweisen, in H2(5%)/Ar-Atmosphäre synthetisiert. Ni12P5, Ni12P5-Ni2P und Ni2P Nanopartikel, die mit einer dünnen Schicht aus Kohlenstoffmaterial beschichtet sind, werden erhalten. Ni12P5-Ni2P und Ni2P Nanopartikel katalysieren die Wasserstoffentwicklungsreaktion (HER) im Sauren effektiv. / High-performance catalysts play a key role in the development of technologies for sustainable production, storage, and conversion of energy. In this thesis, transition-metal-based catalysts, including TiO2/carbon composites, hybrid organic-inorganic NiFe phosphonates, and Ni phosphides are synthesized, characterized, and investigated in photocatalytic or electrocatalytic reactions.
TiO2 is frequently combined with carbon materials, such as reduced graphene oxide (rGO), to produce composites with improved properties. TiO2 is more efficiently stabilized at the surface of rGO than amorphous carbon. Rapid heating of the reaction mixture results in a stronger coupling between the nanoparticles and carbon, more uniform coatings, and smaller particles with narrower size distributions. The more efficient attachment of the oxide leads to better photocatalytic performance.
Layered hybrid NiFe-phenylphosphonate compounds are synthesized in benzyl alcohol, and their oxygen evolution reaction (OER) performance in alkaline medium is investigated. The hybrid particles transformed in situ into NiFe hydroxide nanosheets. X-ray absorption spectroscopy measurements suggest the metal sites in the active catalyst inherited partly the distorted coordination. The combination of the synergistic effect between Ni and Fe with the structural properties of the hybrid results in an efficient catalyst that generates a current density of 10 mA cm-2 at an overpotential of 240 mV.
Moreover, nickel phosphides are synthesized through thermal treatment under H2(5%)/Ar of layered nickel phenyl- or methylphosphonates that act as single-source precursors. Ni12P5, Ni12P5-Ni2P and Ni2P nanoparticles coated with a thin shell of carbonaceous material are produced. Ni12P5-Ni2P and Ni2P NPs efficiently catalyze the hydrogen evolution reaction (HER) in acidic medium. Co2P and CoP NPs are also synthesized following this method.
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