Photodeposition-Based Synthesis of TiO2@IrOx Core-Shell Catalyst for Proton Exchange Membrane Water Electrolysis with Low Iridium Loading.

The widespread application of green hydrogen production technologies requires cost reduction of crucial elements. To achieve this, a viable pathway to reduce the iridium loading in proton exchange membrane water electrolysis (PEMWE) is explored. Herein, a scalable synthesis method based on a photodeposition process for a TiO2@IrOx core-shell catalyst with a reduced iridium content as low as 40 wt.% is presented. Using this synthesis method, titania support particles homogeneously coated with a thin iridium oxide shell of only 2.1 ± 0.4 nm are obtained. The catalyst exhibits not only high ex situ activity, but also decent stability compared to commercially available catalysts. Furthermore, the unique core-shell structure provides a threefold increased electrical powder conductivity compared to structures without the shell. In addition, the low iridium content facilitates the fabrication of sufficiently thick catalyst layers at decreased iridium loadings mitigating the impact of crack formation in the catalyst layer during PEMWE operation. It is demonstrated that the novel TiO2@IrOx core-shell catalyst clearly outperforms the commercial reference in single-cell tests with an iridium loading below 0.3 mgIr cm-2 exhibiting a superior iridium-specific power density of 17.9 kW gIr -1 compared to 10.4 kW gIr -1 for the commercial reference.

Tethered Alkylammonium Dications as Electrochemical Interface Modifiers: Chain Length Effect on CO2 Reduction Selectivity at Industry-Relevant Current Density.

The electrochemical reduction of CO2 (CO2RR) has the potential to be an economically viable method to produce platform chemicals synergistically with renewable energy sources. Copper is one of the most commonly used electrocatalysts for this purpose, as it allows C-C bond formation, yielding a broad product distribution. Controlling selectivity is a stepping stone on the way to its industrial application. The kinetics of the reaction can be modified to favor the rates of certain products quickly and inexpensively by applying additives such as ionic liquids and coelectrolytes that directly affect the electrocatalytic interface. In this work, we propose tethered tetraalkylammonium salts as double-charged cationic modifiers of the electrochemical double layer to control CO2RR product selectivity. A novel setup comprising a gas diffusion electrode (GDE) flow cell coupled with real-time mass spectroscopy was used to study the effect of a library of the selected salts. We emphasize how the length of an alkyl linker effectively controls the selectivity of the reaction toward C1, C2, or C3 products at high relevant current densities (Jtotal = -400 mA cm-2) along with the inhibition of the parasitic hydrogen evolution reaction. Standard long-term experiments were performed for quantitative validation and stability evaluation. These results have broad implications for further tailoring an effective catalytic system for selective CO2 reduction reaction.

Stability of Bimetallic PtxRuy - From Model Surfaces to Nanoparticulate Electrocatalysts.

Fundamental research campaigns in electrocatalysis often involve the use of model systems, such as single crystals or magnetron-sputtered thin films (single metals or metal alloys). The downsides of these approaches are that oftentimes only a limited number of compositions are picked and tested (guided by chemical intuition) and that the validity of trends is not verified under operating conditions typically present in real devices. These together can lead to deficient conclusions, hampering the direct application of newly discovered systems in real devices. In this contribution, the stability of magnetron-sputtered bimetallic PtxRuy thin film electrocatalysts (0 at. % to 100 at. % Ru content) along with three commercially available carbon-supported counterparts (50-67 at. % Ru content) was mapped under electrocatalytic conditions in acidic electrolytes using online ICP-MS. We found several differences between the two systems in the amount of metals dissolved along with the development of the morphology and composition. While the Pt-rich PtxRuy compositions remained unchanged, 30-50 nm diameter surface pits were detected in the case of the Ru-rich sputtered thin films. Contrastingly, the surface of the carbon-supported NPs enriched in Pt accompanied by the leaching of a significant amount of Ru from the alloy structure was observed. Change in morphology was accompanied by a mass loss reaching around 1-2 wt % in the case of the sputtered samples and almost 10 wt % for the NPs. Since PtxRuy has prime importance in driving alcohol oxidation reactions, the stability of all investigated alloys was screened in the presence of isopropanol. While Pt dissolution was marginally affected by the presence of isopropanol, several times higher Ru dissolution was detected, especially in the case of the Ru-rich compositions. Our results underline that trends in terms of electrocatalytic activity and stability cannot always be transferred from model samples to systems that are closer to the ones applied in real devices.

The Role of Alkali Cations on the Selectivity of 5-Hydroxymethylfurfural Electroreduction on Glassy Carbon.

In the past decade, organic electrosynthesis has emerged as an atom- and energy-efficient strategy for harvesting renewable electricity that provides exceptional control over the reaction parameters. A profound and fundamental understanding of electrochemical interfaces becomes imperative to advance the knowledge-based development of electrochemical processes. The major strategy toward an efficient electrochemical system is based on the advancement in material science for electrocatalysis. Studies on the complex interplay among electrode surface, electrolyte, and transformation intermediates have only recently started to emerge. It involves acquiring atomic-scale insights into the electrochemical double layer, for which the identity and concentration of composing ions play a crucial role. In this study, we present how the identity and concentration of alkali cations impact the selectivity of aldehyde functionality electroreduction. As a case-study transformation, we set the electrochemical conversion of 5-hydroxymethylfurfural (HMF), a promising biomass-derived feedstock for the sustainable production of polymer or fuel precursors. Our findings reveal a consistent trend of the selectivity shift towards 2,5-bis(hydroxymethyl)furan (BHMF) as a function of cation size and concentration, rationalized by specific cation adsorption at the glassy carbon (GC), followed by the increase in the electrode surface charge density.

Few-layer black phosphorus enables nitrogen fixation under ambient conditions.

Nitrogen (N2) fixation is a key reaction in biological and industrial chemistry, which does not occur spontaneously under ambient conditions but often depends on very specific catalysts and harsh reaction processes. Here we show that exposing exfoliated black phosphorus to the open air triggers, concomitantly, the oxidation of the two-dimensional (2D) material and the fixation of up to 100 parts per million (0.01%) of N2 on the surface. The fixation also occurs in pristine non-exfoliated material. Besides, other allotropic forms of phosphorus, like red P, also fixes N2 during ambient oxidation, suggesting that the N2 fixation process is intrinsic with phosphorus oxidation and does not depend on the chemical structure or the dimensionality of the solid. Despite the low amounts of N2 fixed, this serendipitous discovery could have fundamental implications on the chemistry and environmental stability of phosphorous and the design of related catalysts for N2 fixation.

Toward High-Energy-Density Fuels for Direct Liquid Organic Hydrogen Carrier Fuel Cells: Electrooxidation of 1-Cyclohexylethanol.

Electrochemically active liquid organic hydrogen carriers (EC-LOHCs) can be used directly in fuel cells; so far, however, they have rather low hydrogen storage capacities. In this work, we study the electrooxidation of a potential EC-LOHC with increased energy density, 1-cyclohexylethanol, which consists of two storage functionalities (a secondary alcohol and a cyclohexyl group). We investigated the product spectrum on low-index Pt single-crystal surfaces in an acidic environment by combining cyclic voltammetry, chronoamperometry, and in situ infrared spectroscopy, supported by density functional theory. We show that the electrooxidation of 1-cyclohexylethanol is a highly structure-sensitive reaction with activities Pt(111) ≫ Pt(100) > Pt(110). Most importantly, we demonstrate that 1-cyclohexylethanol can be directly converted to acetophenone, which desorbs from the electrode surface. However, decomposition products are formed, which lead to poisoning. If the latter side reactions could be suppressed, the electrooxidation of 1-cyclohexylethanol would enable the development of EC-LOHCs with greatly increased hydrogen storage capacities.

Contribution of Electrolyte Decomposition Products and the Effect of Temperature on the Dissolution of Transition Metals from Cathode Materials.

A fundamental understanding of aging processes in lithium-ion batteries (LIBs) is imperative in the development of future battery architectures for widespread electrification. Herein, dissolution of transition metals from cathode active materials of LIBs is among the most important degradation processes. Research has demonstrated that elevated operating temperatures accelerate battery degradation. However, the exact mechanism of transition-metal dissolution at elevated temperatures has still to be clarified. Current literature suggests that the reaction rate of dissolution increases with increasing temperature; moreover, the decomposition of electrolytes results in products that also accelerate dissolution processes. Most studies focus on ex situ analyses of thermally treated full cells. This approach is not appropriate to get detailed insights and to distinguish between different contributions. In this work, with the help of real-time dissolution analysis using an electroanalytical flow cell (EFC) coupled to an inductively coupled plasma mass spectrometer (ICP-MS), we present novel details of the temperature effects on in situ dissolution at the cathode electrolyte interface. With fresh electrolytes, we find increased Mn dissolution even at open-circuit conditions as well as with constant voltage polarization when the electrode sample is heated at constant temperatures between 50 and 80 °C. The release of transition metals also responds in a nuanced manner when applying temperature transients. Utilizing electrolytes preheated at 60 and 100 °C, we demonstrate that decomposition products in the bulk electrolyte have no influence on transition-metal (TM) dissolution when constantly flushing the cell with the thermally aged electrolyte samples. Only when keeping the cathode temperature at 60 °C, the dissolution increases by a factor of 2-3. Our findings highlight the interplay between the cathode and electrolyte and provide new insights into the dissolution mechanism of cathode materials.

Tailoring Cu Electrodes for Enhanced CO2 Electroreduction through Plasma Electrolysis in Non-Conventional Phosphorus-Oxoanion-Based Electrolytes.

This study presents a green, ultra-fast, and facile technique for the fabrication of micro/nano-structured and porous Cu electrodes through in-liquid plasma electrolysis using phosphorous-oxoanion-based electrolytes. Besides the preferential surface faceting, the Cu electrodes exhibit unique surface structures, including octahedral nanocrystals besides nanoporous and microporous structures, depending on the employed electrolyte. The incorporation of P-atoms into the Cu surfaces is observed. The modified Cu electrodes display increased roughness, leading to higher current densities for CO2 electroreduction reaction. The selectivity of the modified Cu electrodes towards C2 products is highest for the Cu electrodes treated in Na2 HPO3 and Na3 PO4 electrolytes, whereas those treated in Na2 H2 PO2 produce the most H2 . The Cu electrode treated in Na3 PO4 produces ethylene (23 %) at -1.1 V vs. RHE, and a comparable amount of acetaldehyde (15 %) that is typically observed for Cu(110) single crystals. The enhanced selectivity is attributed to several factors, including the surface morphology, the incorporation of phosphorus into the Cu structure, and the formation of Cu(110) facets. Our results not only advance our understanding of the influence of the electrolyte's nature on the plasma electrolysis of Cu electrodes, but also underscores the potential of in-liquid plasma treatment for developing efficient Cu electrocatalysts for sustainable CO2 conversion.

Oxygen Reduction Reaction in Alkaline Media Causes Iron Leaching from Fe-N-C Electrocatalysts.

The electrochemical activity of modern Fe-N-C electrocatalysts in alkaline media is on par with that of platinum. For successful application in fuel cells (FCs), however, also high durability and longevity must be demonstrated. Currently, a limited understanding of degradation pathways, especially under operando conditions, hinders the design and synthesis of simultaneously active and stable Fe-N-C electrocatalysts. In this work, using a gas diffusion electrode half-cell coupled with inductively coupled plasma mass spectrometry setup, Fe dissolution is studied under conditions close to those in FCs, that is, with a porous catalyst layer (CL) and at current densities up to -125 mA·cm-2. Varying the rate of the oxygen reduction reaction (ORR), we show a remarkable linear correlation between the Faradaic charge passed through the electrode and the amount of Fe dissolved from the electrode. This finding is rationalized assuming that oxygen reduction and Fe dissolution reactions are interlinked, likely through a common intermediate formed during the Fe redox transitions in Fe species involved in the ORR, such as FeNxCy and Fe3C@N-C. Moreover, such a linear correlation allows the application of a simple metric─S-number─to report the material's stability. Hence, in the current work, a powerful tool for a more applied stability screening of different electrocatalysts is introduced, which allows on the one hand fast performance investigations under more realistic conditions, and on the other hand a more advanced mechanistic understanding of Fe-N-C degradation in CLs.

CO2 Electroreduction on Silver Foams Modified by Ionic Liquids with Different Cation Side Chain Length.

Ionic liquids (ILs) are capable of tuning the kinetics of electroreduction processes by modifying a catalyst interface. In this work, a group of hydrophobic imidazolium-based ILs were immobilized on Ag foams by using a procedure known as "solid catalyst with ionic liquid layer" (SCILL). The derived electrocatalysts demonstrated altered selectivity and CO production rates for the electrochemical reduction of CO2 compared to the unmodified Ag foam. The activity change caused by the IL was dependent on the length of the N-alkyl substituent. The rate of CO production is optimized at moderate chain length and IL loadings. The observed trends are attributed to a local enrichment of CO2-based species in the proximity of the catalyst and a modification of the environment of its active sites. On the contrary, high loadings or long IL chains render the surface inaccessible and favor the hydrogen evolution reaction.

On-line Electrode Dissolution Monitoring during Organic Electrosynthesis: Direct Evidence of Electrode Dissolution during Kolbe Electrolysis.

Electrode dissolution was monitored in real-time during Kolbe electrolysis along with the characteristic products. The fast determination of appropriate reaction conditions in electro-organic chemistry enables the minimization of electrode degradation while keeping an eye on the optimal formation rate and distribution of products. Herein, essential parameters influencing the dissolution of the electrode material platinum in a Kolbe electrolysis were pinpointed. The formation of reaction products and soluble platinum species were monitored during potentiodynamic and potentiostatic experiments using an electroanalytical flow cell coupled to two different mass spectrometers. The approach opens new vistas in the field of electro-organic chemistry because it enables precise and quick quantification of dissolved metals during electrosynthesis, also involving electrode materials other than platinum. Furthermore, it draws attention to the vital topic of electrode stability in electro-organic synthesis, which becomes increasingly important for the implementation of green chemical processes utilizing renewable energy.

Engineering gold-platinum core-shell nanoparticles by self-limitation in solution.

Core-shell particles with thin noble metal shells represent an attractive material class with potential for various applications ranging from catalysis to biomedical and pharmaceutical applications to optical crystals. The synthesis of well-defined core-shell architectures remains, however, highly challenging. Here, we demonstrate that atomically-thin and homogeneous platinum shells can be grown via a colloidal synthesis method on a variety of gold nanostructures ranging from spherical nanoparticles to nanorods and nanocubes. The synthesis is based on the exchange of low binding citrate ligands on gold, the reduction of platinum and the subsequent kinetically hindered growth by carbon monoxide as strong binding ligand. The prerequisites for homogeneous growth are low core-binding ligands with moderate fast ligand exchange in solution, a mild reducing agent to mitigate homonucleation and a strong affinity of a second ligand system that can bind to the shell's surface. The simplicity of the described synthetic route can potentially be adapted to various other material libraries to obtain atomically smooth core-shell systems.

Electroreductive 5-Hydroxymethylfurfural Dimerization on Carbon Electrodes.

The electrochemical conversion of biomass-based compounds to fuels and fuel precursors can aid the defossilization of the transportation sector. Herein, the electrohydrodimerization of 5-hydroxymethylfurfural (HMF) to the fuel precursor 5,5'-bis(hydroxymethyl)hydrofuroin (BHH) was investigated on different carbon electrodes. Compared to boron-doped diamond (BDD) electrodes, on glassy carbon (GC) electrodes a less negative HMF reduction onset potential and a switch in product selectivity from BHH to the electrocatalytic hydrogenation product 2,5-di(hydroxymethyl)furan (DHMF) with increasing overpotential was found. On BDD, the electrohydrodimerization was the dominant process independent of the applied potential. An increase in the initial HMF concentration led to suppression of the competing hydrogen evolution reaction and DHMF formation, resulting in higher BHH faradaic efficiencies. In contrast, BHH selectivity decreased with higher initial HMF concentration, which was attributed to increased electrochemically induced HMF degradation. Finally, it was demonstrated that even a simple graphite foil can function as an active HMF electroreduction catalyst.

Single-Atom Catalysts: A Perspective toward Application in Electrochemical Energy Conversion.

Single-atom catalysts (SACs) hold great promise for maximized metal utilization, exceptional tunability of the catalytic site, and selectivity. Moreover, they can substantially contribute to lower the cost and abundancy challenges associated with raw materials. Significant breakthroughs have been achieved over the past decade, for instance, in terms of synthesis methods for SACs, their catalytic activity, and the mechanistic understanding of their functionality. Still, great challenges lie ahead in order to render them viable for application in important fields such as electrochemical energy conversion of renewable electrical energy. We have identified three particular development fields for advanced SACs that we consider crucial, namely, the scale-up of the synthesis, the understanding of their performance in real devices such as fuel cells and electrolyzers, and the understanding and mitigation of their degradation. In this Perspective, we review recent activities of the community and provide our outlook with respect to the aspects required to bring SACs toward application.

Online Monitoring of Transition-Metal Dissolution from a High-Ni-Content Cathode Material.

The dissolution of transition metals (TMs) from cathode materials and their deposition on the anode represents a serious degradation process and, with that, a shortcoming of lithium-ion batteries. It occurs particularly at high charge voltages (>4.3 V), contributing to severe capacity loss and thus impeding the increase of cell voltage as a simple measure to increase energy density. We present here for the first time the online detection of dissolved TMs from a Ni-rich layered oxide cathode material with unprecedented potential and time resolution in potentiodynamic scans. To this aid, we used the coupling of an electroanalytical flow cell (EFC) with inductively coupled plasma mass spectrometry (ICP-MS), which is demonstrated to be an ideal tool for a fast performance assessment of new cathode materials from initial cycles. The simultaneous analysis of electrochemical and dissolution data allows hitherto hidden insights into the processes' characteristics and underlying mechanisms.

Implementation of an enclosed ionization interface for the analysis of liquid sample streams with direct analysis in real time mass spectrometry.

RATIONALE: The development of an interface to analyze liquid sample streams with direct analysis in real time mass spectrometry (DART-MS) is of great interest for coupling various analytical techniques, using non-volatile salts, with MS. Therefore, we devised an enclosed ionization interface and a sample introduction system for the versatile analysis of liquid samples with DART-MS. METHODS: The sample introduction system consists of a nebulizer, a spray chamber and a transfer line, while the confined ionization interface is created by implementing a cross-shaped housing between ion source outlet and mass spectrometer inlet. Methodical studies of the effects of various setup parameters on signal intensity and peak shape were conducted, while its diverse applicability was demonstrated by coupling with high-performance liquid chromatography (HPLC) for the analysis of alcohols, organic acids and furanic compounds. RESULTS: The confinement of the ionization interface results in a robust setup design with a well-defined ionization region for focusing of the sprayed sample mist. Thereby, an increase in analyte signal intensity by three orders of magnitude and improved signal stability and reproducibility were obtained in comparison with a similar open ionization interface configuration. Additionally, the successful quantification of alcohols could be demonstrated as well as the compatibility of the setup with HPLC gradient elution. CONCLUSIONS: A versatile setup design for the analysis of liquid sample streams with DART-MS was devised for monitoring reactions or hyphenating analytics with MS. The design minimizes interferences from the laboratory surroundings as well as allows for safe handling of hazardous and toxic chemicals, which renders it suitable for a broad range of applications.

Platinum Dissolution in Realistic Fuel Cell Catalyst Layers.

Pt dissolution has already been intensively studied in aqueous model systems and many mechanistic insights have been gained. Nevertheless, transfer of new knowledge to real-world fuel cell systems is still a significant challenge. To close this gap, we present a novel in situ method combining a gas diffusion electrode (GDE) half-cell with inductively coupled plasma mass spectrometry (ICP-MS). With this setup, Pt dissolution in realistic catalyst layers and the transport of dissolved Pt species through Nafion membranes were evaluated directly. We observed that 1) specific Pt dissolution increased significantly with decreasing Pt loading, 2) in comparison to experiments on aqueous model systems with flow cells, the measured dissolution in GDE experiments was considerably lower, and 3) by adding a membrane onto the catalyst layer, Pt dissolution was reduced even further. All these phenomena are attributed to the varying mass transport conditions of dissolved Pt species, influencing re-deposition and equilibrium potential.

Accessing In Situ Photocorrosion under Realistic Light Conditions: Photoelectrochemical Scanning Flow Cell Coupled to Online ICP-MS.

High-impact photoelectrode materials for photoelectrochemical (PEC) water splitting are distinguished by synergistically attaining high photoactivity and stability at the same time. With numerous efforts toward optimizing the activity, the bigger challenge of tailoring the durability of photoelectrodes to meet industrially relevant levels remains. In situ photostability measurements hold great promise in understanding stability-related properties. Although different flow systems coupled to light-emitting diodes were introduced recently to measure time-resolved photocorrosion, none of the measurements were performed under realistic light conditions. In this paper, a photoelectrochemical scanning flow cell connected to an inductively coupled plasma mass spectrometer (PEC-ICP-MS) and equipped with a solar simulator, Air Mass 1.5 G filter, and monochromator was developed. The established system is capable of independently assessing basic PEC metrics, such as photopotential, photocurrent, incident photon to current efficiency (IPCE), and band gap in a high-throughput manner as well as the in situ photocorrosion behavior of photoelectrodes under standardized and realistic light conditions by coupling it to an ICP-MS. Polycrystalline platinum and tungsten trioxide (WO3) were used as model systems to demonstrate the operation under dark and light conditions, respectively. Photocorrosion measurements conducted with the present PEC-ICP-MS setup revealed that WO3 starts dissolving at 0.8 VRHE with the dissolution rate rapidly increasing past 1.2 VRHE, coinciding with the onset of the saturation photocurrent. The most detrimental damage to the photoelectrode is caused when subjecting it to a prolonged high potential hold, e.g., at 1.5 VRHE. By using standardized illumination conditions such as Air Mass 1.5 Global under 1 Sun, the obtained dissolution characteristics are translatable to actual devices under realistic light conditions. The gained insights can then be utilized to advance synthesis and design approaches of novel PEC materials with improved photostability.

Different Photostability of BiVO4 in Near-pH-Neutral Electrolytes.

Photoelectrochemical water splitting is a promising route to produce hydrogen from solar energy. However, corrosion of photoelectrodes remains a fundamental challenge for their implementation. Here, we reveal different dissolution behaviors of BiVO4 photoanode in pH-buffered borate, phosphate, and citrate (hole-scavenger) electrolytes, studied in operando employing an illuminated scanning flow cell. We demonstrate that decrease in photocurrents alone does not reflect the degradation of photoelectrodes. Changes in dissolution rates correlate to the evolution of surface chemistry and morphology. The correlative measurements on both sides of the liquid-semiconductor junction provide quantitative comparison and mechanistic insights into the degradation processes.