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The integration of metal oxide nanomaterials with mesoporous silica is a promising approach to exploiting the advantages of both types of materials. Traditional synthesis methods typically require multiple steps. This work instead presents a fast, one-step, template-free method for the synthesis of metal oxides homogeneously dispersed within mesoporous silica, including oxides of W, Ti, Nb, Ta, Sn, and Mo. These composites have tunable metal oxide contents, large surface areas, and wide mesopores. The combination of Nb2O5 nanoparticles (NPs) with SiO2 results in an increased surface area and a larger number of acid sites compared to pure Nb2O5 NPs. The surface texture and acidity of the silica–niobia composites can be tuned by adjusting the Nb/Si molar ratio. Moreover, the silica provides protection to the niobia NPs, preventing sintering during thermal treatment at 400 °C. The silica–niobia materials exhibit superior performance as catalysts in the aldol condensation of furfural (Fur) with acetone compared to pure niobia, leading to an up to 62% in product yield. Additionally, these catalysts show remarkable stability, retaining their performance over multiple runs. This work demonstrates the potential of the proposed synthesis approach for preparing more sustainable, high-performance, durable, and stable nanoscale metal oxide-based catalysts with a tunable composition, surface area, and active site density., CICECO—Aveiro Institute of Materials, FCT, Peer Reviewed

Chiral inorganic superstructures have received considerable interest due to the chiral communication between inorganic compounds and chiral organic additives. However, the demanding fabrication and complex multilevel structure seriously hinder the understanding of chiral transfer and self‐assembly mechanisms. Herein, we use chiral CuO superstructures as a model system to study the formation process of hierarchical chiral structures. Based on a simple and mild synthesis route, the time‐resolved morphology and the in situ chirality evolution could be easily followed. The morphology evolution of the chiral superstructure involves hierarchical assembly, including primary nanoparticles, intermediate bundles, and superstructure at different growth stages. Successive redshifts and enhancements of the CD signal support chiral transfer from the surface penicillamine to the inorganic superstructure. Full‐field electro‐dynamical simulations reproduced the structural chirality and allowed us to predict its modulation. This work opens the door to a large family of chiral inorganic materials where chiral molecule‐guided self‐assembly can be specifically designed to follow a bottom‐up chiral transfer pathway., National Natural Science Foundation of China http://dx.doi.org/10.13039/501100001809, Helmholtz-OCPC Postdoc Program, Peer Reviewed

Atomic‐level manipulation of catalysts is important for both fundamental studies and practical applications. Here, the central metal atom in an atomically precise Ag25 nanocluster (NC) is replaced with a single Pd, Pt, and Au atom, respectively, and employed as a model system to study the structure–property–activity relationship at the atomic level. While the geometric structures are well‐preserved after doping, the electronic structures of Ag25 NCs are significantly altered. The combination of Ag25 and TiO2 enhances the charge separation at the interface, exhibiting a 10 times higher hydrogen production rate in photocatalytic hydrogen evolution reaction compared to bare TiO2. Further results show that heteroatoms doping has a negative impact on performance, particularly in the cases of Pd and Au doping. Ultraviolet photoelectron spectroscopy measurements and density functional theory calculations suggest that the lower activities are due to an energy mismatch between the levels of doped NCs and TiO2. These findings not only reveal the impact of heteroatoms doping on the electronic properties and photocatalytic activities of NCs, but can also guide the design of heterometallic NCs for photocatalytic applications., Heteroatoms doping alters the electronic structures of Ag25 nanoclusters (NCs), while keeping the geometric structures unchanged. In this way, the geometrical effects and the electronic effects are clearly distinguished. The photocatalytic activities of as‐prepared NCs deposited onto TiO2 are investigated. The performances follow the order of Ag25 ≥ PtAg24 > PdAg24 ≥ AuAg24. image © 2023 WILEY‐VCH GmbH, DFG http://dx.doi.org/10.13039/501100001659, China Scholarship Council http://dx.doi.org/10.13039/501100004543, Peer Reviewed

This article was supported by the German Research Foundation (DFG) and the Open Access Publication Fund of Humboldt-Universität zu Berlin., Atomic layer deposition (ALD) is a deposition technique well-suited to produce high-quality thin film materials at the nanoscale for applications in transistors. This review comprehensively describes the latest developments in ALD of metal oxides (MOs) and chalcogenides with tunable bandgaps, compositions, and nanostructures for the fabrication of high-performance field-effect transistors. By ALD various n-type and p-type MOs, including binary and multinary semiconductors, can be deposited and applied as channel materials, transparent electrodes, or electrode interlayers for improving charge-transport and switching properties of transistors. On the other hand, MO insulators by ALD are applied as dielectrics or protecting/encapsulating layers for enhancing device performance and stability. Metal chalcogenide semiconductors and their heterostructures made by ALD have shown great promise as novel building blocks to fabricate single channel or heterojunction materials in transistors. By correlating the device performance to the structural and chemical properties of the ALD materials, clear structure–property relations can be proposed, which can help to design better-performing transistors. Finally, a brief concluding remark on these ALD materials and devices is presented, with insights into upcoming opportunities and challenges for future electronics and integrated applications.

Entropy‐stabilized oxides (ESOs), such as (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)O, have recently gained significant interest as novel anodes for lithium‐ion batteries (LIBs) due to their stable crystal structure and robust lithium‐storage properties. In this work, (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)O oxides with different morphologies are prepared by electrospinning and solvothermal method and are applied as anode active materials for LIBs. It is found that different morphologies possess different characteristics, namely particle size, particle size range, and defect density, which have a significant effect on the electrochemical behavior. The most active (Mg, Co, Ni, Cu, Zn) ESO shows outstanding electrochemical properties in terms of high reversible capacity (480 mAh g–1 at 20 mA g–1), superior rate capability (206 mAh g–1 at 2 A g–1), and excellent cycling stability (390 mAh g–1 at 500 mA g–1 after 300 cycles). The strategy demonstrates the importance of engineering microstructures in tailoring the electrochemical performance., Entropy‐stabilized (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)O oxides with different particle size, particle size range, and defect density are prepared by electrospinning and solvothermal method and tested as anode active materials for lithium‐ion batteries. The most active (Mg0.2Co0.2Ni0.2Cu0.2Zn0.2)O oxide shows high reversible capacity, superior rate capability, and excellent cycling stability. image, Ministry of University and Research, China Scholarship Council http://dx.doi.org/10.13039/501100004543, Peer Reviewed

This article was supported by the German Research Foundation (DFG) and the Open Access Publication Fund of Humboldt-Universität zu Berlin., Atomic layer deposition (ALD) is a deposition technique well-suited to produce high-quality thin film materials at the nanoscale for applications in transistors. This review comprehensively describes the latest developments in ALD of metal oxides (MOs) and chalcogenides with tunable bandgaps, compositions, and nanostructures for the fabrication of high-performance field-effect transistors. By ALD various n-type and p-type MOs, including binary and multinary semiconductors, can be deposited and applied as channel materials, transparent electrodes, or electrode interlayers for improving charge-transport and switching properties of transistors. On the other hand, MO insulators by ALD are applied as dielectrics or protecting/encapsulating layers for enhancing device performance and stability. Metal chalcogenide semiconductors and their heterostructures made by ALD have shown great promise as novel building blocks to fabricate single channel or heterojunction materials in transistors. By correlating the device performance to the structural and chemical properties of the ALD materials, clear structure–property relations can be proposed, which can help to design better-performing transistors. Finally, a brief concluding remark on these ALD materials and devices is presented, with insights into upcoming opportunities and challenges for future electronics and integrated applications.

A thermal atomic layer deposition (ALD) process to fabricate MoS2 thin films is successfully demonstrated by using cycloheptatriene molybdenum tricarbonyl (C7H8Mo(CO)3) and H2S as precursors at an ALD temperature below 300 °C. The process is systematically investigated, showing a typical self‐limiting characteristic within an ALD temperature window of 225–285 °C and a high growth‐per‐cycle of 0.11 nm. The as‐deposited films are amorphous while they can be crystallized in situ by sulfurization with H2S at a low temperature of 300 °C. A prototypical application of the developed ALD process is demonstrated by constructing a MoS2/TiO2 heterostructure through depositing MoS2 onto anodized TiO2 nanotubes for photoelectrochemical water splitting. The MoS2/TiO2 heterostructures exhibit approximately three times superior photoelectrochemical performance than the pristine TiO2 nanotubes. This is attributed to an enhanced visible light‐harvesting ability of MoS2 and an improved separation of the photo‐generated charge carriers at the heterostructure interface, which is affirmed by a staggering gap (type II) between MoS2 and TiO2 as probed by ultraviolet photoelectron spectroscopy., Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659, Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659, Peer Reviewed

Rational design of cost‐effective, high performance and stable hydrogen evolution reaction (HER) electrocatalysts in both acidic and alkaline media holds the key to the future hydrogen‐based economy. Herein, we introduce an effective approach of simultaneous non‐metal (S) and metal (Fe or Mn) doping of MoP to achieve excellent HER performance at different pH. The catalysts show remarkable overpotentials at −10 mA cm−2 of only 65 and 68 mV in 0.5 M H2SO4, and 50 and 51 mV in 1.0 M KOH, respectively, as well as much higher turnover frequencies compared to undoped MoP. Furthermore, the catalysts exhibit outstanding long‐term stability at a fixed current of −10 mA cm−2 for 40 h. The effects of both dopants, such as electronic structure modification and enhancement of the intrinsic activity, increase of the electrochemically active surface area, and formation of coordinatively unsaturated edge sites, act cooperatively to accelerate the HER at both pH media. Additionally, the presence of oxophilic Mn and Fe at the surface results in Mn or Fe oxide/hydroxide species that promote the dissociation of water molecules in alkaline electrolyte. This work introduces a facile and effective design principle that could pave the way towards engineering highly active HER catalysts for a wide pH range., Metal (Mn or Fe) and non‐metal (S) dual doped MoP catalysts were synthesiszed by reductive pyrolysis of the corresponding Mn,Mo‐ and Fe,Mo‐phosphonates precursors, in the presence of elemental S. The derived catalysts showed remarkable hydrogen evolution reaction (HER) activity in acidic and alkaline media. The dual doping process endowed MoP with proper hydrogen binding energy thus enhancing the HER in acidic media. In addition, Mn and Fe acted as surface oxides species in alkaline medium, which facilitated the water dissociation step. image, Yousef Jameel Scholarship Fund, Peer Reviewed

Nanocomposites of TiO2 and carbon nanotubes (CNTs) have been extensively studied in photocatalysis, sensing, and energy conversion and storage over the last decade. The unique properties of these nanocomposites are greatly dependent on the morphology, crystallinity, and homogeneity of the TiO2 coating. However, a fine control of the film microstructure is still challenging due to limited understanding of early stages of the TiO2 growth. The presence of an intermediate buffer layer can induce remarkable changes in the morphological and structural characteristics of the coatings. Here, TiO2 films deposited by atomic layer deposition (ALD) on CNTs without and with different intermediate layers (Al2O3 and ZnO) have been systematically investigated. Compared to bare CNTs, it is suggested that these two intermediate layers with higher surface energy can lead to a delay of the TiO2 crystallization, ultimately resulting in the growth of conformal and crystalline TiO2 films. This study demonstrates a strategy to tailor the microstructure and the properties of thin films via ALD by applying intermediate layers and provides information about the role of surface energy of the substrate in crystallization and growth behavior of ALD thin films., Peer Reviewed

Rational design of cost‐effective, high performance and stable hydrogen evolution reaction (HER) electrocatalysts in both acidic and alkaline media holds the key to the future hydrogen‐based economy. Herein, we introduce an effective approach of simultaneous non‐metal (S) and metal (Fe or Mn) doping of MoP to achieve excellent HER performance at different pH. The catalysts show remarkable overpotentials at −10 mA cm−2 of only 65 and 68 mV in 0.5 M H2SO4, and 50 and 51 mV in 1.0 M KOH, respectively, as well as much higher turnover frequencies compared to undoped MoP. Furthermore, the catalysts exhibit outstanding long‐term stability at a fixed current of −10 mA cm−2 for 40 h. The effects of both dopants, such as electronic structure modification and enhancement of the intrinsic activity, increase of the electrochemically active surface area, and formation of coordinatively unsaturated edge sites, act cooperatively to accelerate the HER at both pH media. Additionally, the presence of oxophilic Mn and Fe at the surface results in Mn or Fe oxide/hydroxide species that promote the dissociation of water molecules in alkaline electrolyte. This work introduces a facile and effective design principle that could pave the way towards engineering highly active HER catalysts for a wide pH range., Metal (Mn or Fe) and non‐metal (S) dual doped MoP catalysts were synthesiszed by reductive pyrolysis of the corresponding Mn,Mo‐ and Fe,Mo‐phosphonates precursors, in the presence of elemental S. The derived catalysts showed remarkable hydrogen evolution reaction (HER) activity in acidic and alkaline media. The dual doping process endowed MoP with proper hydrogen binding energy thus enhancing the HER in acidic media. In addition, Mn and Fe acted as surface oxides species in alkaline medium, which facilitated the water dissociation step. image, Yousef Jameel Scholarship Fund, Peer Reviewed

One-dimensional (1D) electrospun nanomaterials have attracted significant attention due to their unique structures and outstanding chemical and physical properties such as large specific surface area, distinct electronic and mass transport, and mechanical flexibility. Over the past years, the integration of metal sulfides with electrospun nanomaterials has emerged as an exciting research topic owing to the synergistic effects between the two components, leading to novel and interesting properties in energy, optics and catalysis research fields for example. In this review, we focus on the recent development of the preparation of electrospun nanomaterials integrated with functional metal sulfides with distinct nanostructures. These functional materials have been prepared via two efficient strategies, namely direct electrospinning and post-synthesis modification of electrospun nanomaterials. In this review, we systematically present the chemical and physical properties of the electrospun nanomaterials integrated with metal sulfides and their application in electronic and optoelectronic devices, sensing, catalysis, energy conversion and storage, thermal shielding, adsorption and separation, and biomedical technology. Additionally, challenges and further research opportunities in the preparation and application of these novel functional materials are also discussed., Peer Reviewed

Earth-abundant Mn-based oxide nanoparticles are supported on carbon nitride using two different immobilization methods and tested for the oxygen reduction reaction. Compared to the metal free CN, the immobilization of Mn oxide enhances not only the electrocatalytic activity but also the selectivity towards the 4e- reduction reaction of O2 to H2O. The XPS analysis reveals the interaction of the pyridine N species with Mn3O4 nanoparticles being particularly beneficial. This interaction is realized—although to a limited extent—when preparing the catalysts via impregnation; via the oleic acid route it is not observed. Whilst this work shows the potential of these systems to catalyze the ORR, the main limiting factor is still the poor conductivity of the support which leads to overpotential., Peer Reviewed

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Earth-abundant Mn-based oxide nanoparticles are supported on carbon nitride using two different immobilization methods and tested for the oxygen reduction reaction. Compared to the metal free CN, the immobilization of Mn oxide enhances not only the electrocatalytic activity but also the selectivity towards the 4e- reduction reaction of O2 to H2O. The XPS analysis reveals the interaction of the pyridine N species with Mn3O4 nanoparticles being particularly beneficial. This interaction is realized—although to a limited extent—when preparing the catalysts via impregnation; via the oleic acid route it is not observed. Whilst this work shows the potential of these systems to catalyze the ORR, the main limiting factor is still the poor conductivity of the support which leads to overpotential., Peer Reviewed

Sections PDFPDF Tools Share Abstract Lithium and sodium thiophosphates (and related compounds) have recently attracted attention because of their potential use as solid electrolytes in solid‐state batteries. These compounds, however, exhibit only limited stability in practice as they react with the electrodes. The decomposition products partially remain redox active hence leading to excess capacity. The redox activity of thiophosphates is explicitly used to act as electrode for sodium‐ion batteries. Copper thiophosphate (Cu3PS4) is used as a model system. The storage behavior between 0.01 and 2.5 V versus Na+/Na is studied in half cells using different electrolytes with 1 m NaPF6 in diglyme showing the best result. Cu3PS4 shows highly reversible charge storage with capacities of about 580 mAh g−1 for more than 200 cycles @120 mA g−1 and about 450 mAh g−1 for 1400 cycles @1 A g−1. The redox behavior is studied by operando X‐ray diffraction and X‐ray photoelectron spectroscopy. During initial sodiation, Cu3PS4 undergoes a conversion reaction including the formation of Cu and Na2S. During cycling, the redox activity seems dominated by sulfur. Interestingly, the capacity of Cu3PS4 for lithium storage is smaller, leading to about 170 mAh g−1 after 200 cycles. The results demonstrate that thiophosphates can lead to reversible charge storage over several hundred cycles without any notable capacity decay., Peer Reviewed

Hierarchical core–shell (C–S) heterostructures composed of a NiO shell deposited onto stacked‐cup carbon nanotubes (SCCNTs) are synthesized by atomic layer deposition (ALD). A film of NiO particles (0.80–21.8 nm in thickness) is uniformly deposited onto the inner and outer walls of the SCCNTs. The electrical resistance of the samples is found to increase of many orders of magnitude with the increasing of the NiO thickness. The response of NiO–SCCNT sensors toward low concentrations of acetone and ethanol at 200 °C is studied. The sensing mechanism is based on the modulation of the hole‐accumulation region in the NiO shell layer upon chemisorption of the reducing gas molecules. The electrical conduction mechanism is further studied by the incorporation of an Al2O3 dielectric layer at NiO and SCCNT interfaces. The investigations on NiO–Al2O3–SCCNT, Al2O3–SCCNT, and NiO–SCCNT coaxial heterostructures reveal that the sensing mechanism is strictly related to the NiO shell layer. The remarkable performance of the NiO–SCCNT sensors toward acetone and ethanol benefits from the conformal coating by ALD, large surface area of the SCCNTs, and the optimized p‐NiO shell layer thickness followed by the radial modulation of the space‐charge region., Peer Reviewed

Efficient synthetic methods to produce high‐performance electrode‐active materials are crucial for developing energy storage devices for large‐scale applications, such as hybrid supercapacitors (HSCs). Here, an effective approach to obtain controllable carbon‐encapsulated T‐Nb2O5 nanocrystals (NCs) is presented, based on the solvothermal treatment of NbCl5 in acetophenone. Two separate condensation reactions of acetophenone generate an intimate and homogeneous mixture of Nb2O5 particles and 1,3,5‐triphenylbenzene (TPB), which acts as a unique carbon precursor. The electrochemical performance of the resulting composites as anode electrode materials can be tuned by varying the Nb2O5/TPB ratio. Remarkable performances are achieved for Li‐ion and Na‐ion energy storage systems at high charge–discharge rates (specific capacities of ≈90 mAh g−1 at 100 C rate for lithium and ≈125 mAh g−1 at 20 C for sodium). High energy and power densities are also achieved with Li‐ and Na‐ion HSC devices constructed by using the Nb2O5/C composites as anode and activated carbon (YPF‐50) as cathode, demonstrating the excellent electrochemical properties of the materials synthesized with this approach., Peer Reviewed

Hierarchical core–shell (C–S) heterostructures composed of a NiO shell deposited onto stacked‐cup carbon nanotubes (SCCNTs) are synthesized by atomic layer deposition (ALD). A film of NiO particles (0.80–21.8 nm in thickness) is uniformly deposited onto the inner and outer walls of the SCCNTs. The electrical resistance of the samples is found to increase of many orders of magnitude with the increasing of the NiO thickness. The response of NiO–SCCNT sensors toward low concentrations of acetone and ethanol at 200 °C is studied. The sensing mechanism is based on the modulation of the hole‐accumulation region in the NiO shell layer upon chemisorption of the reducing gas molecules. The electrical conduction mechanism is further studied by the incorporation of an Al2O3 dielectric layer at NiO and SCCNT interfaces. The investigations on NiO–Al2O3–SCCNT, Al2O3–SCCNT, and NiO–SCCNT coaxial heterostructures reveal that the sensing mechanism is strictly related to the NiO shell layer. The remarkable performance of the NiO–SCCNT sensors toward acetone and ethanol benefits from the conformal coating by ALD, large surface area of the SCCNTs, and the optimized p‐NiO shell layer thickness followed by the radial modulation of the space‐charge region., Peer Reviewed

Efficient synthetic methods to produce high‐performance electrode‐active materials are crucial for developing energy storage devices for large‐scale applications, such as hybrid supercapacitors (HSCs). Here, an effective approach to obtain controllable carbon‐encapsulated T‐Nb2O5 nanocrystals (NCs) is presented, based on the solvothermal treatment of NbCl5 in acetophenone. Two separate condensation reactions of acetophenone generate an intimate and homogeneous mixture of Nb2O5 particles and 1,3,5‐triphenylbenzene (TPB), which acts as a unique carbon precursor. The electrochemical performance of the resulting composites as anode electrode materials can be tuned by varying the Nb2O5/TPB ratio. Remarkable performances are achieved for Li‐ion and Na‐ion energy storage systems at high charge–discharge rates (specific capacities of ≈90 mAh g−1 at 100 C rate for lithium and ≈125 mAh g−1 at 20 C for sodium). High energy and power densities are also achieved with Li‐ and Na‐ion HSC devices constructed by using the Nb2O5/C composites as anode and activated carbon (YPF‐50) as cathode, demonstrating the excellent electrochemical properties of the materials synthesized with this approach., Peer Reviewed

Hierarchical core–shell (C–S) heterostructures composed of a NiO shell deposited onto stacked‐cup carbon nanotubes (SCCNTs) are synthesized by atomic layer deposition (ALD). A film of NiO particles (0.80–21.8 nm in thickness) is uniformly deposited onto the inner and outer walls of the SCCNTs. The electrical resistance of the samples is found to increase of many orders of magnitude with the increasing of the NiO thickness. The response of NiO–SCCNT sensors toward low concentrations of acetone and ethanol at 200 °C is studied. The sensing mechanism is based on the modulation of the hole‐accumulation region in the NiO shell layer upon chemisorption of the reducing gas molecules. The electrical conduction mechanism is further studied by the incorporation of an Al2O3 dielectric layer at NiO and SCCNT interfaces. The investigations on NiO–Al2O3–SCCNT, Al2O3–SCCNT, and NiO–SCCNT coaxial heterostructures reveal that the sensing mechanism is strictly related to the NiO shell layer. The remarkable performance of the NiO–SCCNT sensors toward acetone and ethanol benefits from the conformal coating by ALD, large surface area of the SCCNTs, and the optimized p‐NiO shell layer thickness followed by the radial modulation of the space‐charge region., Peer Reviewed

The morphology of metal oxide nanostructures influences the response of the materials in a given application. In addition to changing the composition, doping can also modify the morphology of a host nanomaterial. Herein, we determine the effect of dopant concentration, reaction temperature, and reaction time on the morphology and assembly of CoxZn1−xO nanoparticles synthesized through non-aqueous sol-gel in benzyl alcohol. With the increase of the atom % of cobalt incorporated from 0 to 15, the shape of the nanoparticles changes from near spherical, to irregular, and finally to triangular. The tendency of the particles to assemble increases in the same direction, with Co0.05Zn0.95O consisting of non-assembled particles, whereas Co0.15Zn0.85O consists of triangular nanoparticles forming spherical structures. The morphology and assembly process are also sensitive to the reaction temperature. The assembly process is found to occur during the nucleation or the early stages of particle growth. The cobalt ions promote the change in the shape during the growth stage of the nanoparticles., Peer Reviewed

The morphology of metal oxide nanostructures influences the response of the materials in a given application. In addition to changing the composition, doping can also modify the morphology of a host nanomaterial. Herein, we determine the effect of dopant concentration, reaction temperature, and reaction time on the morphology and assembly of CoxZn1−xO nanoparticles synthesized through non-aqueous sol-gel in benzyl alcohol. With the increase of the atom % of cobalt incorporated from 0 to 15, the shape of the nanoparticles changes from near spherical, to irregular, and finally to triangular. The tendency of the particles to assemble increases in the same direction, with Co0.05Zn0.95O consisting of non-assembled particles, whereas Co0.15Zn0.85O consists of triangular nanoparticles forming spherical structures. The morphology and assembly process are also sensitive to the reaction temperature. The assembly process is found to occur during the nucleation or the early stages of particle growth. The cobalt ions promote the change in the shape during the growth stage of the nanoparticles., Peer Reviewed

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.

In der vorliegenden Arbeit wird das Prinzip der chemischen Oberflächenmodifikation als allgemeine Synthesestrategie beschrieben. Davon ausgehend werden verschiedene Ansätze der chemischen Funktionalisierung dargestellt, mit denen die Eigenschaften der erhaltenen Materialien eingestellt werden können. Im Fokus der Arbeit stehen Eisenoxid-Nanopartikel, die über die „Benzylalkohol-Route“ dargestellt werden. Es wird auf Basis dieser einfachen und vielseitig anwendbaren Funktionalisierung die Herstellung von neuartigen Hybridmaterialien gezeigt. Zur Funktionalisierung zweier magnetischer molekularer Rezeptoren wurde eine Synthesestrategie entwickelt, bei der organische Gruppen kovalent angebunden wurden. Der erste Rezeptor kann zur Erkennung von Biomarkern und den Metaboliten von Pharmazeutika eingesetzt werden. Die Beschichtung der Oberflächen der Eisenoxid-Nanopartikel gelang dabei durch die Verwendung von Organosilan-basierten Kopplungsreagenzien. Der zweite Rezeptor konnte zur Auftrennung eines racemischen Gemisches eines chiralen cavitand eingesetzt werden. Die Darstellung von Graphenoxid-Eisenoxid-Kompositen gelang erfolgreich durch ein ex-situ Verfahren. Es wurde der Einfluss der Oberflächenfunktionalitäten auf die Beladung und Verteilung der Eisenoxid-Nanopartikel untersucht. Dazu wurden via Diazoniumchemie verschiedene Funktionalitäten auf der Graphenoxid-Oberfläche eingeführt. Die Entwicklung einer wasserfreien one-pot Synthese von Gold-Eisenoxid-hetero-Nanostrukturen beschrieben wurde. Insbesondere wurden die Auswirkungen kleiner organischer Moleküle auf die Bildung der Heterostrukturen untersucht., This thesis describes diverse approaches of chemical functionalization as a general strategy to tailor material properties depending on the target application. Particular attention was dedicated to the surface chemistry of iron oxide nanoparticles. Crystalline 10 nm-sized magnetite nanoparticles synthesized through the “benzyl alcohol route” exhibit superparamagnetic behaviour. For this reason they are regarded as suitable solid supports for the fabrication of recoverable devices, which is a fundamental requirement for several of the reported studies. Here it is demonstrated, via the fabrication of novel hybrid materials, that the ease of functionalization of iron oxide nanoparticles renders this material a versatile platform for the development of diverse surface chemistries. A covalent organic functionalization strategy was developed for the synthesis of two recoverable magnetic molecular receptors. The first targeted the recognition of drugs metabolites and biomarkers. It is based on the use of organosilanes coupling agents. A second approach aimed to the heterogeneous resolution of a racemic mixture of an inherently chiral cavitand. Graphene oxide-iron oxide composites were successfully fabricated through an ex-situ approach based on non-covalent interactions between the component phases. The effects of surface functionalities on the loading and distribution of iron oxide nanoparticles were studied by introducing selected functionalities at the graphene oxide surface through diazonium chemistry. Finally, the development of a non-aqueous one-pot synthesis route to gold-iron oxide hetero-nanostructures was described. Particular emphasis was dedicated to study the influence of small organic molecules in promoting the formation of the heterostructures.

Useful bio-products are obtainable via the catalytic conversion of biomass or derived intermediates as renewable carbon sources. In particular, furanic ethers and levulinate esters (denoted bioEs) have wide application profiles and can be synthesised via acid-catalysed reactions of intermediates such as fructose, 5-hydroxymethyl-2-furaldehyde (HMF) and furfuryl alcohol (FA) with ethanol. Solid acid catalysts are preferred for producing the bioEs with environmental benefits. Furthermore, the versatility of the catalyst in obtaining the bioEs from different intermediates is attractive for process economics, and in the case of porous catalysts, large pore sizes can be beneficial for operating in the kinetic regime. Carbon-based materials are attractive acid catalysts due to their modifiable surface, e.g. with relatively strong sulfonic acid groups (SO3H). Considering these aspects, here, we report the preparation of mesoporous (SO3H)-functionalised-carbon/silica (C/S) composites with large pores and high amounts of acid sites (up to 2.3 mmol g−1), and their application as versatile solid acid catalysts for producing bioEs from fructose, HMF and FA. The mesoporous composites were prepared by activation of an organic compound deposited on the ordered mesoporous silicas MCF (mesostructured cellular foam) and SBA-15, where the organic compound (p-toluenesulfonic acid) acted simultaneously as the carbon and SO3H source. The atomic-level characterisation of the acid nature and strengths was performed by 31P solid-state NMR studies of an adsorbed base probe, in combination with FT-IR and XPS. Comparative catalytic studies showed that the C/S composites are interesting catalysts for obtaining bioEs in high yields, in comparison with classical solid acid catalysts such as sulfonic acid resin Amberlyst™-15 and nanocrystalline (large pore) zeolite H-beta., Peer Reviewed

Available open access thanks to the RSC Gold for Gold initiative. Shared according to the terms set out in the CC licence., Useful bio-products are obtainable via the catalytic conversion of biomass or derived intermediates as renewable carbon sources. In particular, furanic ethers and levulinate esters (denoted bioEs) have wide application profiles and can be synthesised via acid-catalysed reactions of intermediates such as fructose, 5-hydroxymethyl-2-furaldehyde (HMF) and furfuryl alcohol (FA) with ethanol. Solid acid catalysts are preferred for producing the bioEs with environmental benefits. Furthermore, the versatility of the catalyst in obtaining the bioEs from different intermediates is attractive for process economics, and in the case of porous catalysts, large pore sizes can be beneficial for operating in the kinetic regime. Carbon-based materials are attractive acid catalysts due to their modifiable surface, e.g. with relatively strong sulfonic acid groups (SO3H). Considering these aspects, here, we report the preparation of mesoporous (SO3H)-functionalised-carbon/silica (C/S) composites with large pores and high amounts of acid sites (up to 2.3 mmol g−1), and their application as versatile solid acid catalysts for producing bioEs from fructose, HMF and FA. The mesoporous composites were prepared by activation of an organic compound deposited on the ordered mesoporous silicas MCF (mesostructured cellular foam) and SBA-15, where the organic compound (p-toluenesulfonic acid) acted simultaneously as the carbon and SO3H source. The atomic-level characterisation of the acid nature and strengths was performed by 31P solid-state NMR studies of an adsorbed base probe, in combination with FT-IR and XPS. Comparative catalytic studies showed that the C/S composites are interesting catalysts for obtaining bioEs in high yields, in comparison with classical solid acid catalysts such as sulfonic acid resin Amberlyst™-15 and nanocrystalline (large pore) zeolite H-beta., Peer Reviewed

Available open access thanks to the RSC Gold for Gold initiative. Shared according to the terms set out in the CC licence., Acid catalysis plays an important role in biomass conversion processes for producing chemicals and fuels. We report a relatively simple procedure for synthesizing versatile, strong acid catalysts based on carbon and carbon–silica composites with sulfonic acid groups. The process involves chemical activation of a sulfonic acid organic precursor at low temperature. The synthesis conditions can be modified to tune the surface composition, texture, and the acid properties of the materials towards superior catalytic performances. Molecular level insights into the nature and strength of the acid sites were gained by combining high resolution XPS and 1H-decoupled 31P MAS NMR spectroscopy of adsorbed triethylphosphine oxide. These materials are effective acid catalysts for the conversion of different biomass-derived chemicals to useful bio products such as furanic ethers and levulinate esters., Peer Reviewed