Investigation of the Photocatalytic Hydrogen Production of Semiconductor Nanocrystal-Based Hydrogels.

Destabilization of a ligand-stabilized semiconductor nanocrystal solution with an oxidizing agent can lead to a macroscopic highly porous self-supporting nanocrystal network entitled hydrogel, with good accessibility to the surface. The previously reported charge carrier delocalization beyond a single nanocrystal building block in such gels can extend the charge carrier mobility and make a photocatalytic reaction more probable. The synthesis of ligand-stabilized nanocrystals with specific physicochemical properties is possible, thanks to the advances in colloid chemistry made in the last decades. Combining the properties of these nanocrystals with the advantages of nanocrystal-based hydrogels will lead to novel materials with optimized photocatalytic properties. This work demonstrates that CdSe quantum dots, CdS nanorods, and CdSe/CdS dot-in-rod-shaped nanorods as nanocrystal-based hydrogels can exhibit a much higher hydrogen production rate compared to their ligand-stabilized nanocrystal solutions. The gel synthesis through controlled destabilization by ligand oxidation preserves the high surface-to-volume ratio, ensures the accessible surface area even in hole-trapping solutions and facilitates photocatalytic hydrogen production without a co-catalyst. Especially with such self-supporting networks of nanocrystals, the problem of colloidal (in)stability in photocatalysis is circumvented. X-ray photoelectron spectroscopy and photoelectrochemical measurements reveal the advantageous properties of the 3D networks for application in photocatalytic hydrogen production.

Morphological Control Over Gel Structures of Mixed Semiconductor-Metal Nanoparticle Gel Networks with Multivalent Cations.

In this work, the influence of two different types of cations on the gel formation and structure of mixed gel networks comprised of semiconductor (namely CdSe/CdS nanorods NR) and Au nanoparticles (NP) as well as on the respective monocomponent gels is investigated. Heteroassemblies built from colloidal building blocks are usually prepared by ligand removal or cross-linking, thus, both the surface chemistry and the destabilising agent play an essential role in the gelation process. Due to the diversity of the composition, morphology, and optical properties of the nanoparticles, a versatile route to fabricate functional heteroassemblies is of great demand. In the present work, the optics, morphology, and gelation mechanism of pure semiconductor and noble metal as well as their mixed nanoparticle gel networks are revealed. The influence of the gelation agents (bivalent and trivalent cations) on the structure-property correlation is elucidated by photoluminescence, X-ray photoelectron spectroscopy, and electron microscopy measurements. The selection of cations drastically influences the nano- and microstructure of the prepared gel network structures driven by the affinity of the cations to the ligands and the nanoparticle surface. This gelation technique provides a new platform to control the formation of porous assemblies based on semiconductor and metal nanoparticles.

Probing Bidirectional Plasmon-Plasmon Coupling-Induced Hot Charge Carriers in Dual Plasmonic Au/CuS Nanocrystals.

Heterostructured Au/CuS nanocrystals (NCs) exhibit localized surface plasmon resonance (LSPR) centered at two different wavelengths (551 and 1051 nm) with a slight broadening compared to respective homostructured Au and CuS NC spectra. By applying ultrafast transient absorption spectroscopy we show that a resonant excitation at the respective LSPR maxima of the heterostructured Au/CuS NCs leads to the characteristic hot charge carrier relaxation associated with both LSPRs in both cases. A comparison of the dual plasmonic heterostructure with a colloidal mixture of homostructured Au and CuS NCs shows that the coupled dual plasmonic interaction is only active in the heterostructured Au/CuS NCs. By investigating the charge carrier dynamics of the process, we find that the observed interaction is faster than phononic or thermal processes (< 100 fs). The relaxation of the generated hot charge carriers is faster for heterostructured nanocrystals and indicates that the interaction occurs as an energy transfer (we propose Landau damping or interaction via LSPR beat oscillations as possible mechanisms) or charge carrier transfer between both materials. Our results strengthen the understanding of multiplasmonic interactions in heterostructured Au/CuS NCs and will significantly advance applications where these interactions are essential, such as catalytic reactions.

Influencing the coupling between network building blocks in CdSe/CdS dot/rod aerogels by partial cation exchange.

The assembly of CdSe/CdS dot/rod nanocrystals (NCs) with variable length of ZnS tips into aerogel networks is presented. To this end, a partial region selective cation exchange procedure is performed replacing Cd by Zn starting at the NC tip. The produced aerogel networks are investigated structurally and optically. The networks of tip-to-tip connected NCs have an intricate band structure with holes confined to the CdSe cores while electrons are delocalized within the CdS also within connected building blocks. However, the ZnS tips act as a barrier of variable length and strength between the NC building blocks partly confining the electrons. This results in NC based aerogel networks with tunable strength of coupling between building blocks.

Temperature and Composition Dependent Optical Properties of CdSe/CdS Dot/Rod-Based Aerogel Networks.

Employing nanocrystals (NCs) as building blocks of porous aerogel network structures allows the conversion of NC materials into macroscopic solid structures while conserving their unique nanoscopic properties. Understanding the interplay of the network formation and its influence on these properties like size-dependent emission is a key to apply techniques for the fabrication of novel nanocrystal aerogels. In this work, CdSe/CdS dot/rod NCs possessing two different CdSe core sizes were synthesized and converted into porous aerogel network structures. Temperature-dependent steady-state and time-resolved photoluminescence measurements were performed to expand the understanding of the optical and electronic properties of these network structures generated from these two different building blocks and correlate their optical with the structural properties. These investigations reveal the influence of network formation and aerogel production on the network-forming nanocrystals. Based on the two investigated NC building blocks and their aerogel networks, mixed network structures with various ratios of the two building blocks were produced and likewise optically characterized. Since the different building blocks show diverse optical response, this technique presents a straightforward way to color-tune the resulting networks simply by choosing the building block ratio in connection with their quantum yield.

Temperature-Sensitive Localized Surface Plasmon Resonance of α-NiS Nanoparticles.

The presented work shows a synthesis route to obtain nanoparticles of the hexagonal α-NiS phase and core-shell particles where the same material is grown onto previously prepared Au seeds. In the bulk, this nickel sulfide phase is known to exhibit a metal-insulator type phase transition (MIT) at 265 K which drastically alters its electrical conductivity. Since the produced nanoparticles show a localized surface plasmon resonance (LSPR) in the visible range of the electromagnetic spectrum, the development of their optical properties depending on the temperature is investigated. This is the first time an LSPR of colloidal nanoparticles is monitored regarding such a transition. The results of UV-vis absorbance measurements show that the LSPR of the particles can be strongly and reversibly tuned by varying the temperature. It can be switched off by cooling the nanoparticles and switched on again by reheating them above the transition temperature. Additional to the phase transition, the temperature-dependent magnetic susceptibility of α-NiS and Au-NiS nanoparticles suggests the presence of different amounts of uncompensated magnetic moments in these compounds that possibly affect the optical properties and may cause the observed quantitative differences in the LSPR response of these materials.

Structural Diversity in Cryoaerogel Synthesis.

Different techniques that enable the selective microstructure design of aerogels without the use of additives are presented. For this, aerogels were prepared from platinum nanoparticle solutions using the cryoaerogelation method, and respective impacts of different freezing times, freezing media, and freezing temperatures were investigated with electron microscopy as well as inductively coupled plasma optical emission spectroscopy. The use of lower freezing temperatures, freezing media with higher heat conductivities, and longer freezing periods led to extremely different network structures with enhanced stability. In detail, materials were created in the shape of lamellar, cellular, and dendritic networks. So far, without changing the building blocks, it was not possible to create the selective morphologies of resulting aerogels in cryoaerogelation. Now, these additive-free approaches enable targeted structuring and will open up new opportunities in the future cryoaerogel design.

Cryoaerogels and Cryohydrogels as Efficient Electrocatalysts.

Additive-free cryoaerogel coatings from noble metal nanoparticles are prepared and electrochemically investigated. By using liquid nitrogen or isopentane as cooling medium, two different superstructures are created for each type of noble metal nanoparticle. These materials (made from the same amount of particles) have superior morphological and catalytic properties as compared to simply immobilized, densely packed nanoparticles. The morphology of all materials is investigated with scanning electron microscopy (SEM). Electrochemically active surface areas (ECSAs) are calculated from cyclic voltammetry measurements. The catalytic activity is studied for the ethanol oxidation reaction (EOR). Both are found to be increased for superstructured materials prepared by cryoaerogelation. Furthermore, cryoaerogels with cellular to dendritic structure that arise from freezing with isopentane show the best catalytic performance and highest ECSA. Moreover, as a new class of materials, cryohydrogels are created for the first time by thawing flash-frozen nanoparticle solutions. Structure and morphology of these materials match with the corresponding types of cryoaerogels and are confirmed via SEM. Even the catalytic activity in EOR is in accordance with the results from cryoaerogel coatings. As a proof of concept, this approach offers a novel platform towards the easier and faster production of cryogelated materials for wet-chemical applications.

Revealing the Correlation of the Electrochemical Properties and the Hydration of Inkjet-Printed CdSe/CdS Semiconductor Gels.

The mobility of charge carriers across a semiconductor-nanoparticle-based 3D network (i.e., a gel) and the interfacial transfer of the charge carriers across the nanoparticle network/electrolyte boundary are elementary processes for applications in the fields of sensing and energy harvesting. The automated manufacturing of electrodes coated with porous networks can be realized by inkjet printing. By simultaneous printing of CdSe/CdS dot-in-rod-shaped nanorods (NRs) and the destabilization reagent, CdSe/CdS gel-network-coated electrodes can be obtained. In this work, the charge carrier mobility of the electrons and the holes within the porous CdSe/CdS nanorod gel network is investigated via photoelectrochemistry. Using linear sweep voltammograms (LSVs) and intensity-modulated photocurrent spectroscopy (IMPS), it is shown that the electron is moving within the tip-to-tip-connected CdSe/CdS NR gel structure, while the holes are trapped in the CdSe seed of the semiconductor heterostructures. Furthermore, the preparation process of gel structures is related to the elementary mechanism of hydration, which can be shown via photoelectrochemical long-term studies.

Reversible cation exchange on macroscopic CdSe/CdS and CdS nanorod based gel networks.

Over the past decades, cation exchange reactions applied to nanoparticles have opened up synthetic pathways to nanocrystals, which were not accessible by other means before. The limitation of cation exchange on the macroscopic scale of bulk materials is given by the limited ion diffusion within the crystal structure. Lyogels or aerogels are macroscopic, highly voluminous, porous materials composed of interconnected nanoscopic building blocks and hence represent a type of bridge between the macroscopic and the nanoscopic world. To demonstrate the feasibility of cation exchange on such macroscopic nanomaterials, the cation exchange on CdSe/CdS core/shell and CdS nanorod based lyogels to Cu2-xSe/Cu2-xS and Cu2-xS and the reversible exchange back to CdSe/CdS and CdS lyogels is presented. These copper-based lyogels can also be used as an intermediate state on the way to other metal chalcogenide-based macroscopic structures. By reversed cation exchange back to cadmium an additional proof is given, that the crystal structures remain unchanged. It is shown that cation exchange reactions can also be transferred to macroscopic objects like aerogels or lyogels. This procedure additionally allows the access of aerogels which cannot be synthesized via direct destabilization of the respective colloidal solutions.

Nanocrystal Aerogels with Coupled or Decoupled Building Blocks.

The influence of interparticle contact in nanoparticle-based aerogel network structures is investigated by selectively connecting or isolating the building blocks inside of the network, thereby coupling and decoupling them in regards to their optical and electronic properties. This is achieved by tuning the synthesis sequence and exchanging the point of shell growth and the point of particle assembly, leading to two distinctly different structures as examined by electron microscopy. By thorough examination of the resulting optical properties of the generated structures, the clear correlation between nanoscopic/microscopic structure and macroscopic optical properties is demonstrated. Temperature-dependent measurements and effective mass approximation calculations support our findings.

Halide ion influence on the formation of nickel nanoparticles and their conversion into hollow nickel phosphide and sulphide nanocrystals.

A dependence of the formation of tri-n-octylphosphine-capped Ni nanocrystals on the presence of halide ions during their synthesis is shown. For the application-oriented synthesis of Ni particles, this information can be crucial. Furthermore, Ni nanoparticles can be converted to nickel phosphide or sulphide by heating them up in the presence of a phosphorus or sulphur source, resulting in either solid or hollow nanocrystals, formed via the nanoscale Kirkendall effect, depending on the synthesis route. By adjusting the Ni crystallite size in the initial nanoparticles via the halide ion concentration the cavity size of the resulting hollow nanocrystals can be tuned, which is otherwise impossible to realise for particles of a similar total diameter by using this process. The synthesised hollow Ni3S2 nanocrystals exhibit a much sharper localised surface plasmon resonance (LSPR) band than all previously presented particles of this material, which is known to show molar extinction coefficients at the LSPR maximum similar to Au. This narrow linewidth could be explained by the nanoparticles' high crystallinity resulting from the Kirkendall process and is interesting for various possible optical applications such as surface-enhanced Raman spectroscopy owing to the low cost of the involved materials compared to the widely used noble metals.

Patterning of Nanoparticle-Based Aerogels and Xerogels by Inkjet Printing.

Nanoparticle-based voluminous 3D networks with low densities are a unique class of materials and are commonly known as aerogels. Due to the high surface-to-volume ratio, aerogels and xerogels might be suitable materials for applications in different fields, e.g. photocatalysis, catalysis, or sensing. One major difficulty in the handling of nanoparticle-based aerogels and xerogels is the defined patterning of these structures on different substrates and surfaces. The automated manufacturing of nanoparticle-based aerogel- or xerogel-coated electrodes can easily be realized via inkjet printing. The main focus of this work is the implementation of the standard nanoparticle-based gelation process in a commercial inkjet printing system. By simultaneously printing semiconductor nanoparticles and a destabilization agent, a 3D network on a conducting and transparent surface is obtained. First spectro-electrochemical measurements are recorded to investigate the charge-carrier mobility within these 3D semiconductor-based xerogel networks.

Photoluminescence Lifetime Based Investigations of Linker Mediated Electronic Connectivity Between Substrate and Nanoparticle.

The evolution of systems based on nanoparticles as the main component seems to be a self-accelerating process during the last five decades. Hence, an overview across this field gets more and more challenging. It is sometimes rewarding to focus on the fundamental physical phenomenon of the electronic interconnection between the different building blocks of the obtained devices. Therefore, the investigation of charge transport among the utilized particles and their substrate is one of the mandatory steps in the development of semiconductor nanoparticle based devices like e.g., sensors and LEDs. The investigation of the influence of tunneling barriers on the properties of nanoparticle-functionalized surfaces is a challenging task. The different basic influences on the charge transport dynamics are often difficult to separate from each other. Non-invasive and easily viable experiments are still required to resolve the charge distributing mechanisms in the systems. In the presented work, we want to focus on thin and transparent indium tin oxide (ITO) layers covered glass slides since this substrate is frequently utilized in nanoelectronics. CdSe/CdS nanorods (NRs) are applied as an optically addressable probe for the electronic surface states of the conductive glass. The presented experimental design provides the proof of electronic interconnections in ITO coated glass/linker/NR electrodes via easy reproducible functionalization and polishing experiments. UV/Vis absorption and photoluminescence (PL) lifetime measurements revealed changes in the optical properties caused by differences in the charge carrier dynamics between the system. Our work is focused on the modification of charge carrier dynamics due to the application of linker molecules with different functional groups like (3-mercaptopropyl)methoxysilane (MPTMS) and (3-aminopropyl)trimethoxysilane (APTMS). The presented observations are explained with a simple kinetic model.

The Interaction of Guest Molecules with Co-MOF-74: A Vis/NIR and Raman Approach.

Co-MOF-74 rod like crystals with a length of several hundred micrometers are synthesized by a solvothermal procedure and their interaction with different gases is evaluated for selective gas sensing. We show strongly anisotropic absorption behavior of the Co-MOF-74 crystals when illuminated with polarized light. The interactions of guests (CO2 , propane, propene, Ar, MeOH, H2 O) with Co-MOF-74, is studied by various spectroscopic techniques. Vis/NIR shows peak shifts of Co-MOF-74 depending on the interaction with the guest. In the visible and the NIR the maximum absorbance is shifted selectively corresponding to the intensity of the CoII -guest interaction. Even propene and propane could be distinguished at room temperature by their different interactions with Co-MOF-74. Raman spectroscopy was used to detect a modified vibrational behavior of Co-MOF-74 upon gas adsorption. We show that the adsorption of H2 O leads to a characteristic shift of the peak maxima in the Raman spectra.

Low Threshold Room Temperature Amplified Spontaneous Emission in 0D, 1D and 2D Quantum Confined Systems.

We address optical amplification properties of quantum nanoparticles of the cadmium selenide/cadmium sulfide (CdSe/CdS) material system with different dimensionality of spatial confinement. CdSe/CdS core/shell quantum dots (QDs), core/shell quantum rods (QRs) and 5 monolayer thick core/crown nanoplatelets (NPLs) at ambient temperature are considered, exhibiting 0D, 1D and 2D spatial confinement dimensionality of the electronic system, respectively. Continuous films of all these nanoparticles are synthesised, and amplified spontaneous emission (ASE) spectra are measured under femtosecond pumping at wavelengths of 400 nm and 800 nm, respectively. The lowest threshold is found for NPLs and the highest for QDs, demonstrating the influence of the rod-like and plate-like CdS structures. To emphasize this effect, ASE is demonstrated also in CdSe/CdS QRs and NPLs under nanosecond pumping at 355 nm in the same material films. The amplification has been achieved without use of any feedback structure, emphazising the efficiency of the antenna effect. The pumping threshold fluences for NPLs and QRs are observed to be similar, but no ASE is observed in QDs up to the damage threshold of the nanoparticle layers. The length variation investigation with nanosecond pumping resulted in the gain coefficients of 29 cm-1 and 37 cm-1 for QRs and NPLs, respectively.

Chloride Ion Mediated Synthesis of Metal/Semiconductor Hybrid Nanocrystals.

A synthetic route to prepare metal-semiconductor hybrid nanoparticles is presented, along with the possibility to tune the ratio of primary to secondary nucleation and the morphology of the semiconductor material grown on the metal nanoparticle seeds. Gold and cobalt-platinum nanoparticles are employed as metal seeds, on which CdS or CdSe is grown. Using transmission electron microscopy, absorption spectroscopy (UV-vis), and powder X-ray diffraction as characterization techniques, a significant influence of chloride ions on the type of nucleation (that is, secondary or primary nucleation) as well as on the shape of the resulting heterostructures is observed. Partially replacing the commonly used cadmium precursor CdO by varying amounts of CdCl2 opens access to rod-like, multiarmed, flower-like, and bullet-like structures. The results suggest that neither pure CdO nor pure CdCl2 as precursors but only a mixture of both make these structures obtainable. In this article, the influence of the chloride ion concentration during semiconductor growth on metal seeds is investigated in depth. The morphology of the resulting heterostructures is characterized carefully, and a growth mechanism is suggested. Furthermore, it is shown that this synthetic approach can be transferred to seeds of various metals such as platinum, gold, and cobalt platinum.

Synthesis of Plasmonic Cu2-x Se@ZnS Core@Shell Nanoparticles.

We report the synthesis of plasmonic Cu2-x Se@ZnS core@shell nanoparticles (NPs). We used a shell growth approach, starting from Cu2-x Se NPs that have been shown before to exhibit a localized surface plasmon resonance (LSPR). By careful synthesis planning we avoided cation exchange reactions and received core@shell nanoparticles that, after oxidation under air, exhibit a strong LSPR in the NIR. Interestingly, the crystalline, closed ZnS shell that we grew with variable thickness still allowed a slow oxidation of the core under ambient conditions, while the core was effectively protected from reduction, even in the presence of reducing agents such as borane tert-butyamine complex and diisobutylaluminum hydride, giving rise to a stable particle LSPR, also under strongly reducing conditions.

Tuning the LSPR in copper chalcogenide nanoparticles by cation intercalation, cation exchange and metal growth.

Localized surface plasmon resonances (LSPRs) of degenerately doped copper chalcogenide nanoparticles (NPs) (Cu2-xSe berzelianite and Cu1.1S covellite) have been modified applying different methods. The comparison of the cation exchange (Cu2-xSe) and intercalation (Cu1.1S) of Ag(I) and Cu(I) has shown that Ag(I) causes a non reversible, air stable shift of the LSPR. This was compared to the influence of Au(I) cation exchange into Cu1.1S platelets under the formation of Cu1.1S-Au2S mixed nanoplatelets. Furthermore, we show the growth of Au domains on Cu2-xSe, and discuss the interaction of the two plasmonic parts of the obtained dual plasmonic Cu2-xSe-Au hybrid particles.

Phase transfer of 1- and 2-dimensional Cd-based nanocrystals.

In this work, luminescent CdSe@CdS dot-in-rod nanocrystals, CdSe@CdS/ZnS nanorods as well as CdSe-CdS core-crown nanoplatelets were transferred into aqueous phase via ligand exchange reactions. For this purpose, bifunctional thiol-based ligands were employed, namely mercaptoacetic acid (MAA), 3-mercaptopropionic acid (MPA), 11-mercaptoundecanoic acid (MUA) as well as 2-(dimethylamino)ethanthiol (DMAET). Systematic investigations by means of photoluminescence quantum yield measurements as well as photoluminescence decay measurements have shown that the luminescence properties of the transferred nanostructures are affected by hole traps (induced by the thiol ligands themselves) as well as by spatial insulation and passivation against the environment. The influence of the tips of the nanorods on the luminescence is, however, insignificant. Accordingly, different ligands yield optimum results for different nanoparticle samples, mainly depending on the inorganic passivation of the respective samples. In case of CdSe@CdS nanorods, the highest emission intensities have been obtained by using short-chain ligands for the transfer preserving more than 50% of the pristine quantum yield of the hydrophobic nanorods. As opposed to this, the best possible quantum efficiency for the CdSe@CdS/ZnS nanorods has been achieved via MUA. The gained knowledge could be applied to transfer for the first time 2-dimensional CdSe-CdS core-crown nanoplatelets into water while preserving significant photoluminescence (up to 12% quantum efficiency).