Michael Schwarze

Boosting Visible‐Light‐Driven Photocatalytic Hydrogen Evolution with an Integrated Nickel Phosphide–Carbon Nitride System

Solar light harvesting by photocatalytic H2 evolution from water could solve the problem of greenhouse gas emission from fossil fuels with alternative clean energy. However, the development of more efficient and robust catalytic systems remains a great challenge for the technological use on a large scale. Here we report the synthesis of a sol-gel prepared mesoporous graphitic carbon nitride (sg-CN) combined with nickel phosphide (Ni2 P) which acts as a superior co-catalyst for efficient photocatalytic H2 evolution by visible light. This integrated system shows a much higher catalytic activity than the physical mixture of Ni2 P and sg-CN or metallic nickel on sg-CN under similar conditions. Time-resolved photoluminescence and electron paramagnetic resonance (EPR) spectroscopic studies revealed that the enhanced carrier transfer at the Ni2 P-sg-CN heterojunction is the prime source for improved activity.

Mesoporous Carbon Nitride-Tungsten Oxide Composites for Enhanced Photocatalytic Hydrogen Evolution

Composites of mesoporous polymeric carbon nitride and tungsten(VI) oxide show very high photocatalytic activity for the evolution of hydrogen from water under visible light and in the presence of sacrificial electron donors. Already addition of very small amounts of WO3 yields up to a twofold increase in the efficiency when compared to bulk carbon nitrides and their composites and more notably even to the best reported mesoporous carbon nitride-based photocatalytic materials. The higher activity can be attributed to the high surface area and synergetic effect of the carbon nitrides and the WO3 resulting in improved charge separation through a photocatalytic solid-state Z-scheme mechanism.

Rhodium catalyzed hydrogenation reactions in aqueous micellar systems as green solvents

The hydrogenation of itaconic acid and dimethyl itaconate is transferred from methanol to aqueous micellar solutions of several surfactants, e.g., SDS and Triton X-100, in order to facilitate the recovery of the catalyst. The reaction rate and selectivity strongly depends on the chosen surfactant and in some cases also on the surfactant concentration. In the best case the selectivity is the same as in methanol but the reaction rate is still lower because of a lower hydrogen solubility in water. Repetitive semi-batch experiments are chosen to demonstrate that high turn-over-numbers (>1000) can be reached in aqueous micellar solutions. No notable catalyst deactivation is observed in these experiments. The performance of micellar reaction systems is controlled by the partition coefficient of the substrates between the micelles and the continuous aqueous phase which can be predicted using the Conductor-like Screening Model for Real Solvents (COSMO-RS).

Microemulsion systems for catalytic reactions and processes

Among the available green solvents, microemulsion systems show superior properties for catalytic reactions and processes which can be easily tuned by the selection of an appropriate surfactant. In this review, we show examples for bio-, homogeneous and heterogeneous catalysis and discuss the parameters which are important for successful implementation of these systems. Based on the kind of catalysis, they allow for the reuse of dissolved catalysts or even for a better solubilisation of hydrophobic reactants. However, their phase behaviour which strongly depends on composition and temperature as well as surfactant/catalyst interaction has to be studied in detail.

Visible light driven non-sacrificial water oxidation and dye degradation with silver phosphates: multi-faceted morphology matters

The convenient synthesis of multi-faceted versus irregular shaped Ag3PO4 microparticles for the visible light driven non-sacrificial water oxidation is reported. Strikingly, the multi-faceted particles are found to be more effective for oxygen evolution reaction (OER) by photocatalytic water oxidation in water and in phosphate buffer solutions as well as for dye degradation in comparison to the irregular shaped particles.

Homogeneous Stabilization of Pt Nanoparticles in Dendritic Core–Multishell Architectures: Application in Catalytic Hydrogenation Reactions and Recycling

Core–multishell architectures are a new approach to homogeneously stabilize metal nanoparticles for harsh conditions. Herein, we present the synthesis and stabilization of Pt nanoparticles in dendritic core–multishell polymers and their application in hydrogenation reactions. The successful recycling of the catalyst was demonstrated for the hydrogenation of methyl crotonate 1 and was either achieved by ultrafiltration or in a two‐phase system for at least 14 cycles. Thereby, the total turnover number (TON) was increased to 22 000. In the recycling experiments, low metal leaching into the product (as low as 0.3 ppm) was detected. Additionally, the selective hydrogenation of isophorone 3 was investigated and selectivities of 99:1 for CC versus CO hydrogenation were achieved.

Diacetylene Functionalized Covalent Organic Framework (COF) for Photocatalytic Hydrogen Generation

Covalent organic frameworks (COFs) are crystalline, highly porous, two- or three-dimensional polymers with tunable topology and functionalities. Because of their higher chemical stabilities in comparison to their boron-linked counterparts, imine or β-ketoenamine linked COFs have been utilized for a broad range of applications, including gas storage, heterogeneous catalysis, energy storage devices, or proton-conductive membranes. Herein, we report the synthesis of highly porous and chemically stable acetylene (-C≡C-) and diacetylene (-C≡C-C≡C-) functionalized β-ketoenamine COFs, which have been applied as photocatalyst for hydrogen generation from water. It is shown that the diacetylene moieties have a profound effect as the diacetylene-based COF largely outperforms the acetylene-based COF in terms of photocatalytic activity. As a combined effect of high porosity, easily accessible diacetylene (-C≡C-C≡C-) functionalities and considerable chemical stability, an efficient and recyclable heterogeneous photocatalytic hydrogen generation is achieved.

Oleylethoxycarboxylate--an efficient surfactant for copper extraction and surfactant recycling via micellar enhanced ultrafiltration.

The nonaoxyethylene oleylether carboxylic acid Akypo RO90 VG, a surfactant with ionic character at high pH and non-ionic character at low pH, has been investigated with respect to copper removal from aqueous streams via micellar enhanced ultrafiltration (MEUF) with subsequent copper and RO90 separation using the method of cloud point extraction (CPE). Almost quantitative Cu2+ removal is obtained in MEUF and more than 90% Cu2+ is separated from RO90 in CPE. The investigation of Cu(2+)/RO90 complexes with small-angle neutron scattering (SANS) shows almost no structural change of RO90 micelles in the presence of Cu2+. These results show the importance of the surfactant head group for optimizing the specific interaction with the ion to be extracted. This optimization and the ability to recycle the surfactant by a temperature variation and using the cloud point phenomenon is an elegant approach to achieve efficient metal ion extraction.

Quasi-homogeneous hydrogenation with platinum and palladium nanoparticles stabilized by dendritic core-multishell architectures.

Platinum and palladium nanoparticles, supported and stabilized by polymeric core-shell architectures, proved to be active catalysts for hydrogenation reactions. Here, two different reactions were used as probes to investigate the influence of the polymeric support: the hydrogenation of α-methyl styrene (AMS) to cumene and the partial hydrogenation of 1,5-cyclooctadiene (COD). We found that the stability of the nanoparticles and the rate of reaction are higher in the presence of a hydrophobic octadecyl shell within a three-shell polymer system. The kinetic study of AMS hydrogenation showed much higher activities for palladium nanoparticles than for platinum nanoparticles, and the obtained results (e.g., 35 kJ/mol for the activation energy) are of the same order of magnitude as reported earlier for palladium supported on alumina. A methanol/n-heptane biphasic mixture was tested for catalyst recycling and allowed for highly efficient catalyst separation with very low metal leaching.

A structurally versatile nickel phosphite acting as a robust bifunctional electrocatalyst for overall water splitting

The design and development of economical and highly efficient electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) under alkaline conditions are vital in lowering the overall energy losses in alkaline water electrolysis. Here we present a nickel phosphite, Ni11(HPO3)8(OH)6, belonging to the unique class of phosphorus-based inorganic materials with striking structural features that have been explored for the first time in the reaction of electrocatalytic overall water splitting with a profound understanding of the system using in situ and ex situ techniques. When electrophoretically deposited, the nickel phosphite exhibited remarkable electrocatalytic activity, yielding considerably low overpotentials for both the OER and HER with extreme structural stability and enhanced durability in alkaline media. Apart from the attractive structural merits, the higher activity of nickel phosphite is mainly attributed to the formation of oxidized nickel species in the catalytic OER process, while subtle experimental evidence of the participation of phosphite anions for the acceleration of the HER with the support of Ni2+ cations as catalytically active sites is identified, which is highly compelling and has never been previously discovered. Finally, the bifunctionality of nickel phosphite was demonstrated by constructing an alkaline water electrolyzer with a low cell voltage and over 4 days of undiminishing stability. This work offers an appealing cost-effective system based on earth-abundant metals for water electrolysis and can be extended to other transition metal based homo- or hetero-bimetallic phosphites.