Homogeneous Metal Research Articles

Self-cleaned surface of vanadium boride for long-lasting and boosted Fenton oxidation

Coupling extra electron supply with iron-mediated advanced oxidation processes (AOPs) is an efficient strategy for long-lasting oxidation of organic contaminants in environmental remediation. Many subsequent attempts have been made, such as homogeneous catalysts and metal catalysts, of which secondary organic pollution and surface passivation layers limit their application. In this work, metal borides as co-catalysts can efficiently accelerate the Fenton reaction by firmly sacrificing electrons to Fe(III) reduction. Among multiple metallic borides, vanadium boride (VB2) performs superiorly as dual active sites to solve the Fe(III) cycle dilemma and quickly generate hydroxyl radicals via Fenton reaction for almost completely eliminating almost carbamazepine (CBZ) in VB2/Fe(III)/H2O2. Characterization analysis and the density functional theory (DFT) calculation unveil that the synergistic effect of V and B on the surface of VB2 makes Fe-O bonds of FeOH2+ weaker (from 173.8 pm to 178.4 pm) to produce more active Fe(III) species. And meanwhile, active Fe(III) can be rapidly reduced into Fe(II) on the surface of VB2 and then be completely released into solution for subsequent Fenton reaction and hydroxyl radical generation. More importantly, VB2 performs steadily and efficiently for 7th consecutive test in VB2/Fe(III)/H2O2 to degrade more than 95% CBZ, resulting from the self-cleaning surface of VB2 to expose reactive regions for persistent electron sacrifice and sustainably stimulative Fenton oxidation. Therefore, this research offers the detailed fundamental perception into the genesis of VB2 as well as a novel electron donor for boosting Fenton oxidation towards water remediation.

Obtaining Symmetrical Gradient Structure in Copper Wire by Combined Processing

Traditionally, structural wire is characterized by a homogeneous microstructure, where the average grain size in different parts of the wire is uniform. According to the classical Hall–Petch relationship, a homogeneous polycrystalline metal can be strengthened by decreasing the average grain size since an increase in the volume fraction of grain boundaries will further impede the motion of dislocations. However, a decrease in the grain size inevitably leads to a decrease in the ductility and deformability of the material due to limited dislocation mobility. Putting a gradient microstructure into the wire has promising potential for overcoming the compromise between strength and ductility. This is proposed a new combined technology in this paper in order to obtain a gradient microstructure. This technology consists of deforming the wire in a rotating equal-channel step die and subsequent traditional drawing. Deformation of copper wire with a diameter of 6.5 mm to a diameter of 5.0 mm was carried out in three passes at room temperature. As a result of such processing, a gradient microstructure with a surface nanostructured layer (grain size ~400 nm) with a gradual increase in grain size towards the center of the wire was obtained. As a result, the microhardness in the surface zone was 1150 MPa, 770 Mpa in the neutral zone, and 685 MPa in the central zone of the wire. Such a symmetrical spread of microhardness, observed over the entire cross-section of the rod, is a direct confirmation of the presence of a gradient microstructure in deformed materials. The strength characteristics of the wire were doubled: the tensile strength increased from 335 MPa to 675 MPa, and the yield strength from 230 MPa to 445 MPa. At the same time, the relative elongation decreased from 20% to 16%, and the relative contraction from 28% to 23%. Despite the fact that the ductility of copper is decreased after cyclic deformation, its values remain at a fairly high level. The validity of all results is confirmed by numerous experiments using a complex of traditional and modern research methods, which include optical, scanning, and transmission microscopy; determination of mechanical properties under tension; and measurement of hardness and electrical resistance. These methods allow reliable interpretation of the fine microstructure of the wire and provide information on its strength, plastic, and electrical properties.

Evaluating sustainable energy pathways: Economic perspective on advanced hydrogen production

This investigation seeks to evaluate hydrogen generation technologies in China with a focus on two commercial processes, namely hydrothermal oxidation and supercritical water gasification of organic waste from 2011 to 2021. This period witnessing major development, and highlight the key determinants of hydrogen production. The present study was mainly concerned with the enhancement of SCWG processes for hydrogen generation from microalgae and other potential feedstock. Some of the significant observations made in this period are the critical role of biomass composition, choice of catalyst, and operating conditions in increasing H-producing capabilities of reactor systems. The authors of research affirm that the feedstock with a high carbohydrate content and low levels of protein are the most suitable for hydrogen generation. Thus, expanding research on Supercritical Water Gasification, there is the development of HTO methods to consider various pathways of hydrogen production and their connection with existing energy networks. It also studied the effects that several types of catalysts embracing the heterogeneous transition metals and the homogeneous alkali metal compounds have on the efficiency of hydrogen production. These changes have rendered the hydrogen generation process to make more precise predictions and/or course corrections on the process. The studies that have been done between 2011 and 2021 show significant improvements in the ways that sustainable and efficient hydrogen generation technology can be created in China. The results provide a solid platform for future improvements and stress positive impacts that can be provided by these technologies for China's sustainability and energy transition progress.

The influence of metal ions on aqueous dispersions of graphite oxide

ABSTRACT The residual metallic impurities in the graphite oxide (GO) dominate their properties and have a negative influence on the potential applications. The swelling of the GO suspensions is mainly affected by electrostatic forces and special interactions between water molecules, metal ions and hydrophilic groups. Bivalent and trivalent cations give rise to ionic crosslinking of the charged network within the particles. The CaCl2 solution has the best purification effect. A new purification method is proposed in the purification process, the origin metal ions in GO suspensions are replaced by homogeneous metal ions first, and GO suspensions are desalted by electrodialysis device. Free ionic calcium is removed by electrodialysis, and only the calcium that interact with GO particles is remained. The content of fixed calcium is 0.0049 g/g (nearly clear) after washing with 1.5 mmol/L CaCl2 solution and electrodialyzing for 20 min. The new method improves the purification efficiency and save energy.

Unlocking the Anion Effect on Steerable Production of 5-Hydroxymethylfurfural.

Homogeneous metal salt catalysts play a pivotal role in industrial production of 5-hydroxymethylfurfural (HMF). Herein, we first proposed the anion effect on steerable production of HMF using metal salts with different anions as catalyst in a biphasic system of tetrahydrofuran (THF)/NaCl aqueous solution (NaCl aq). Notably, the anions affected the catalytic activity of the metal salts, leading to an order of magnitude difference in the HMF yields, i.e., AlBr3 (74.0 mol %)>AlCl3 (60.8 mol %)>Al2(SO4)3 (35.2 mol %)>Al(NO3)3 (14.9 mol %). The anion effect on steerable production of HMF could be attributed to the proximity effect and electron tension. Anions form close-range interactions with glucose molecules by proximity effect to promote electron transfer, facilitating the isomerization of glucose to fructose. Besides, anions induce a reduction of the electron cloud density of glucose carbon atoms, generating electron tension that rapidly transforms glucose from the ground state to the transition state, thereby increasing the HMF yield. Based on the revelation of anions effect and evaluation of techno-economic process, we expect to provides theoretical guidance for high-throughput screening of metal salt catalysts in industrial biorefinery.

Synergistic hardening in a dual phase high‐entropy (Hf,Nb,Ta,Ti,Zr)C–(Hf,Nb,Ta,Ti,Zr)B2 ultra‐high temperature ceramic

AbstractA dual phase high‐entropy (Hf,Nb,Ta,Ti,Zr)C–(Hf,Nb,Ta,Ti,Zr)B2 ultra‐high temperature ceramic was synthesized using a single step boro‐carbothermal reduction route. The synthesized powder was densified by spark plasma sintering at 2000°C, resulting in complete solid solution formation and a relative density of ≈99%. The dual phase ceramic was 43 vol% high‐entropy carbide and 57 vol% high‐entropy boride. The grain sizes were 0.85 ± 0.34 µm for the carbide and 0.87 ± 0.33 µm for the boride with minimal residual oxide (0.2 vol%) detected in the microstructure. The resulting composition had a higher microhardness than the individual boride and carbide ceramics across the range of testing loads with maximum hardness of 47.5 ± 4 GPa at a load of 0.49N. The high hardness is attributed to the minimum residual oxide, submicron grains, favorable carbide‐to‐boride ratio, homogeneous metal distribution within the phases, uniform microstructure, and synergistic dual phase hardening.

Development of Group IV Metal Complexes Bearing Thioether-Amido Ligands with Enhanced High-Temperature Catalytic Performance toward Olefin Copolymerization.

The development of homogeneous metal catalysts with both high activity and exceptional thermal stability is crucial for the efficient synthesis of polyolefin elastomers (POEs) through solution-phase olefin polymerization. In this study, a series of Hf (Hf1-Hf5), Zr (Zr1), and Ti (Ti1) complexes featuring thioether-amido ligands were synthesized and carefully characterized using advanced techniques such as 1H and 13C NMR spectroscopy as well as single-crystal X-ray diffraction analysis for Hf4 and Hf5. The results revealed that the catalytic activity and 1-octene incorporation efficiency of these metal complexes followed the trend Hf > Zr > Ti, underscoring the significant impact of the metal center on catalytic performance. Furthermore, the choice of ligands was found to play a critical role in dictating the catalytic properties, with ligands bearing less steric hindrance on the sulfur atom proving to be more favorable for copolymerization reactions. Notably, the Hf complex Hf1, featuring a methyl group on the sulfur atom, displayed exceptional catalytic activity as high as 21,060 kg(polymer)·mol-1(Hf)·h-1 toward ethylene/1-octene copolymerization at 120 °C and produced POE with a high molecular weight (Mw = 6.3 × 104 g·mol-1), relatively narrow distribution (Đ = 2.4), and high incorporation of 1-octene (34.1 mol %). This study demonstrates the potential of tailored ligand design in developing efficient metal catalysts for the production of high-value-added POEs.

Advancing Heterogeneous Organic Synthesis With Coordination Chemistry-Empowered Single-Atom Catalysts.

For traditional metal complexes, intricate chemistry is required to acquire appropriate ligands for controlling the electron and steric hindrance of metal active centers. Comparatively, the preparation of single-atom catalysts is much easier with more straightforward and effective accesses for the arrangement and control of metal active centers. The presence of coordination atoms or neighboring functional atoms on the supports' surface ensures the stability of metal single-atoms and their interactions with individual metal atoms substantially regulate the performance of metal active centers. Therefore, the collaborative interaction between metal and the surrounding coordination environment enhances the initiation of reaction substrates and the formation and transformation of crucial intermediate compounds, which imparts single-atom catalysts with significant catalytic efficacy, rendering them a valuable framework for investigating the correlation between structure and activity, as well as the reaction mechanism of catalysts in organic reactions. Herein, comprehensive overviews of the coordination interaction for both homogeneous metal complexes and single-atom catalysts in organic reactions are provided. Additionally, reflective conjectures about the advancement of single-atom catalysts in organic synthesis are also proposed to present as a reference for later development.

Picolinic acid-mediated Mn(II) activated periodate for ultrafast and selective degradation of emerging contaminants: Key role of high-valent Mn-oxo species

The utilization of periodate (PI, IO4-) in metal-based advanced oxidation processes (AOPs) for the elimination of emerging contaminants (ECs) have garnered significant attention. However, the commonly used homogeneous metal catalyst Mn(II) performs inadequately in activating PI. Herein, we exploited a novel AOP technology by employing the complex of Mn(II) with the biodegradable picolinic acid (PICA) to activate PI for the degradation of electron-rich pollutants. The performance of the Mn(II)-PICA complex surpassed that of ligand-free Mn(II) and other Mn(II) complexes with common aminopolycarboxylate ligands. Through scavenger, sulfoxide-probe transformation, and 18O isotope-labeling experiments, we confirmed that the dominant reactive oxidant generated in the Mn(II)-PICA/PI system was high-valent manganese-oxo species (Mn(V)=O). Due to its reliance on Mn(V)=O, the Mn(II)-PICA/PI process exhibited remarkable selectivity and strong anti-interference during EC oxidation in complex water matrices. Nine structurally diverse pollutants were selected for evaluation, and their lnkobs values in the Mn(II)-PICA/PI system correlated well with their electrophilic/nucleophilic indexes, EHOMO, and vertical IP (R2 = 0.79–0.94). Additionally, IO4- was converted into non-toxic iodate (IO3-) without producing undesired iodine species such as HOI, I2, and I3-. This study provides a novel protocol for metal-based AOPs using PI in combination with chelating agents and high-valent metal-oxo species formation during water purification.

High-Entropy Metal-Organic Frameworks (HEMOFs): A New Frontier in Materials Design for CO2 Utilization.

High-entropy materials (HEMs) emerged as promising candidates for a diverse array of chemical transformations, including CO2 utilization. However, traditional HEMs catalysts are nonporous, limiting their activity to surface sites. Designing HEMs with intrinsic porosity can open the door toward enhanced reactivity while maintaining the many benefits of high configurational entropy. Here, a synergistic experimental, analytical, and theoretical approach to design the first high-entropy metal-organic frameworks (HEMOFs) derived from polynuclear metal clusters is implemented, a novel class of porous HEMs that is highly active for CO2 fixation under mild conditions and short reaction times, outperforming existing heterogeneous catalysts. HEMOFs with up to 15 distinct metals are synthesized (the highest number of metals ever incorporated into a single MOF) and, for the first time, homogenous metal mixing within individual clusters is directly observed via high-resolution scanning transmission electron microscopy. Importantly, density functional theory studies provide unprecedented insight into the electronic structures of HEMOFs, demonstrating that the density of states in heterometallic clusters is highly sensitive to metal composition. This work dramatically advances HEMOF materials design, paving the way for further exploration of HEMs and offers new avenues for the development of multifunctional materials with tailored properties for a wide range of applications.

Synergistic effects of Fe2O3 supported on dendritic fibrous SBA-15 for superior photocatalytic degradation of methylene blue

Environmental pollution caused by dye effluent has attracted much attention, and thus developing photocatalysts with superior photodegradation performance is an imperative task. A series of Fe supported on dendritic fibrous SBA-15 (Fe/DFSBA-15) catalysts with various Fe contents were prepared using a microemulsion coupled with ultrasonic-assisted impregnation methods. The findings revealed that the structural stability of DFSBA-15 was unaffected by the amount of Fe loaded. As the Fe loading increased, the size of Fe2O3 nanocrystals increased while the catalysts’ surface area decreased. The bandgap energy of the catalyst decreased with increasing Fe loading and became constant after reaching an optimal Fe loading of 10 wt%. The one-factor-at-a-time study revealed that 10Fe/DFSBA-15 degraded 94.72 % of methylene blue (MB) within 180 min at 1.5 g/L catalyst dosage, pH 8, and 10 mg/L of concentration, owing to Si-O-Fe coordination, modest Fe2O3 crystallite size, homogeneous metal distribution, slower recombination rate, and low bandgap energy. The advantageous features of 10Fe/DFSBA-15 resulted in accelerating the photodegradation rate, where 10Fe/DFSBA-15 is found as the optimal catalyst. The addition of Fe particles to the DFSBA-15 largely improved their photocatalytic activity toward MB degradation, making it a potential candidate for removing pollutants from aqueous solutions.

Enhanced mineralization of pharmaceutical residues at circumneutral pH by heterogeneous electro-Fenton-like process with Cu/C catalyst

Conventional electro-Fenton (EF) process at acidic pH ∼3 is recognized as a highly effective strategy to degrade organic pollutants; however, homogeneous metal catalysts cannot be employed in more alkaline media. To overcome this limitation, pyrolytic derivatives from metal-organic frameworks (MOFs) have emerged as promising heterogeneous catalysts. Cu-based MOFs were prepared using trimesic acid as the organic ligand and different pyrolysis conditions, yielding a set of nano-Cu/C catalysts that were analyzed by conventional methods. Among them, XPS revealed the surface of the Cu/C-A2-Ar/H2 catalyst was slightly oxidized to Cu(I) and, combined with XRD and HRTEM data, it can be concluded that the catalyst presents a core-shell structure where metallic copper is embedded in a carbon layer. The antihistamine diphenhydramine (DPH), spiked into either synthetic Na2SO4 solutions or actual urban wastewater, was treated in an undivided electrolytic cell equipped with a DSA-Cl2 anode and a commercial air-diffusion cathode able to electrogenerate H2O2. Using Cu/C as suspended catalyst, DPH was completely degraded in both media at pH 6–8, outperforming the EF process with Fe2+ catalyst at pH 3 in terms of degradation rate and mineralization degree thanks to the absence of refractory Fe(III)-carboxylate complexes that typically decelerate the TOC abatement. From the by-products detected by GC/MS, a reaction sequence for DPH mineralization is proposed.

Covalent Organic Framework Catalyzed Amide Synthesis Directly from Alcohol Under Red Light Excitation.

The dehydrogenative coupling of alcohols and amines to form amide bonds is typically catalysed by homogeneous transition metal catalysts at high temperatures ranging from 130-140 °C. In our pursuit of an efficient and recyclable photocatalyst capable of conducting this transformation at room temperature, we report herein a COF-mediated dehydrogenative synthesis. The TTT-DHTD COF was strategically designed to incorporate a high density of functional units, specifically dithiophenedione, to trap photogenerated electrons and effectively facilitate hydrogen atom abstraction reactions. The photoactive TTT-DHTD COF, synthesized using solvothermal methods showed high crystallinity and moderate surface area, providing an ideal platform for heterogeneous amide synthesis. Light absorption by the COF across the entire visible range, narrow band gap, and valence band position make it well-suited for the efficient generation of excitons necessary for targeted dehydrogenation. Utilizing red light irradiation and employing extremely low loading of the COF, we have successfully prepared a wide range of amides, including challenging secondary amides, in good to excellent yields. The substrates' functional group tolerance, very mild reaction conditions, and the catalyst's significant recyclability represent substantial advancements over prior methodologies.

Covalent Organic Framework Catalyzed Amide Synthesis Directly from Alcohol Under Red Light Excitation

AbstractThe dehydrogenative coupling of alcohols and amines to form amide bonds is typically catalysed by homogeneous transition metal catalysts at high temperatures ranging from 130–140 °C. In our pursuit of an efficient and recyclable photocatalyst capable of conducting this transformation at room temperature, we report herein a COF‐mediated dehydrogenative synthesis. The TTT‐DHTD COF was strategically designed to incorporate a high density of functional units, specifically dithiophenedione, to trap photogenerated electrons and effectively facilitate hydrogen atom abstraction reactions. The photoactive TTT‐DHTD COF, synthesized using solvothermal methods showed high crystallinity and moderate surface area, providing an ideal platform for heterogeneous amide synthesis. Light absorption by the COF across the entire visible range, narrow band gap, and valence band position make it well‐suited for the efficient generation of excitons necessary for targeted dehydrogenation. Utilizing red light irradiation and employing extremely low loading of the COF, we have successfully prepared a wide range of amides, including challenging secondary amides, in good to excellent yields. The substrates’ functional group tolerance, very mild reaction conditions, and the catalyst's significant recyclability represent substantial advancements over prior methodologies.

Upcycling of waste acrylonitrile butadiene styrene as N-doped carbocatalyst for peroxymonosulfate-induced degradation by solvothermal process

Advanced upcycling of post-consumer waste plastics into functional carbocatalyst has emerged rapidly as a strategy for simultaneously achieving waste plastics disposal and alternative catalysts fabrication. In this study, this type of magnetic N-doped carbocatalyst hybrid was fabricated by a facile solvothermal impregnation of metallic nitrates into waste acrylonitrile butadiene styrene polymer. The key point of the process was that solvothermal impregnation remarkably enhanced a homogeneous metal dispersion and graphitic N structure was stably introduced into carbocatalyst due to N heteroatoms in inherent structure of waste plastics. It was found that carbocatalyst with predominant encapsulation of magnetic CoFe2O4, Fe0.64Ni0.36 and CoFe possessed excellent catalytic performance to activate peroxymonosulfate with substantial degradation of 98.3% synthetic azo contaminant. Mechanism study indicated that graphitic N and metal species exhibited strong synergistic effects for peroxymonosulfate activation to generate SO4·−, ·OH and 1O2. This system achieves a dual-pathway degradation and electron transfer from azo contaminant to peroxymonosulfate to dominate degradation of azo contaminant, providing a new insight into magnetic carbocatalyst confinement from plastic scrap for peroxymonosulfate activation and its versatile application in wastewater reclamation.

Composition-Dependent Dynamics of Nickel-Iron-Cobalt Metal Catalysts for Oxygen Evolution Reaction

Water electrolyzers, such as proton exchange membrane water electrolyzers (PEM) and anion exchange membrane water electrolyzers (AEM) are important technologies for sustainable electrochemical energy conversion. The oxygen evolution reaction (OER) at the anode is a pivotal half-reaction in these systems. Despite substantial progress over the years, OER kinetics remain a major source of inefficiency in these devices, necessitating the development of stable catalysts. Currently, precious metal-based catalysts dominate the landscape of OER catalysts for these devices. As non-precious alternatives, nickel-iron (Ni/Fe) catalysts have emerged as particularly promising in alkaline conditions. However, they exhibit dynamic behavior during electrocatalysis—for instance, oxidizing to an active oxyhydroxide phase during the OER. This dynamic nature makes it challenging to establish clear structure-activity-stability relationships. Incorporating cobalt (Co) into the catalyst composition has been found to influence the activity and material conversion of mixed Ni-Fe-Co oxides and (oxy)hydroxides. Methods for rationally activating and stabilizing Ni-Fe-based catalysts via electrochemical and chemical (e.g. composition) routes are necessary for enhancing scalability and accessibility in hydrogen production devices.Herein, our goal is to understand and exploit activation protocols to enhance the OER performance of as-synthesized nickel-iron-cobalt metal thin films, addressing three primary objectives: synthesizing and characterizing homogeneous metal catalysts, investigating the impact of different potential ranges and scan rates on catalyst oxidation and surface conversion from the metal, and assessing how the addition of cobalt influences conversion rates and current density of the catalyst. We use cyclic voltammetry to facilitate and disentangle conversion (integrated reductive peak for Ni and/or Co2+ → 3+ transition) and OER performance (current density (mA cm-2) at η = 350 mV). For all compositions tested of (Ni80Fe20)100-xCox, x = 0 - 5 % we observe that the most effective conversion requires both redox and oxygen evolution. To further investigate the relationship between conversion and performance catalysts were tested in varying electrolytes such as 1M KOH, 0.1M KOH, and an ionomer overlayer to understand how these impacted conversion.Subsequently, post-analysis techniques such as X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometry optical emission spectroscopy (ICP-OES) were conducted to gain insights into the surface composition and elemental distribution of the catalysts following potential cycling. Additionally, electrochemical mass spectrometry (EC-MS) was employed to quantify the faradaic efficiency of oxygen, providing an understanding of at what point the catalyst begins converting and how much of the OER current is directed towards OER versus metal conversion.This project advances the fundamental understanding of NiFeCo catalyst conversion, shedding light on the critical role of catalyst composition and investigating the conditions that foster optimal conversion efficiency. The use of physical vapor deposition for thin film catalysts offers distinct advantages, making deposition and scaling processes facile. This capability, coupled with the gained insights into conversion dynamics, sets the stage for in situ optimization of the surface to achieve the active oxyhydroxide phase with the highest performance for AEM water electrolysis.

Asymmetric Hydrogenation of Ketones by Simple Alkane-Diyl-Based Ir(P,N,O) Catalysts: A Comparative Study.

The development of new chiral ligands with simple and modular structure represents a challenging direction in the design of efficient homogeneous transition metal catalysts. Herein, we report on the asymmetric hydrogenation of prochiral ketones catalyzed by the iridium complexes of simple alkane-diyl-based P,N,O-type chiral ligands with a highly modular structure. The role of (i) the P-N and N-O backbone in the potentially tridentate ligands, (ii) the number, position and relative configuration of their stereogenic elements and (iii) the effect of their NH and OH subunits on the activity and enantioselectivity of the catalytic reactions are studied. The systematic variation in the ligand structure and the comparative catalytic experiments shed light on different mechanistic aspects of the iridium-catalyzed reaction. The catalysts containing the simple alkane-diyl-based ligands with central chirality provided high enantioselectivities (up to 98% ee) under optimized reaction conditions and proved to be active and selective even at very high substrate concentrations (100 mmol substrate/mL solvent).

On the existence of a very metal-poor disc in the Milky Way

ABSTRACT The question of whether the Milky Way’s disc extends to low metallicity has been the subject of debate for many years. We aim to address the question by employing a large sample of giant stars with radial velocities and homogeneous metallicities based on the Gaia Data Release 3 BP/RP(XP) spectra. We study the 3D velocity distribution of stars in various metallicity ranges, including the very metal-poor (VMP) regime ($\mathrm{[M/H]} < -2.0$). We find that a clear, stand-alone disc population, i.e. that with a ratio of rotational velocity to velocity dispersion $v/\sigma > 1$, starts to emerge only around $\mathrm{[M/H]} \sim -1.3$, and is not visible for $\mathrm{[M/H]} < -1.6$. Using Gaussian mixture modelling, we show that there are two halo populations in the VMP regime: one stationary and one with a net prograde rotation of $\sim\!\! 80\ \mathrm{km\, s}^{-1}$. In this low-metallicity range, we are able to place constraints on the contribution of a rotation-supported thick disc sub-population to a maximum of $\sim\!\! 3$ per cent in our sample. We compare our results to previous claims of discy VMP stars in both observations and simulations and find that having a prograde halo component could explain most of these.

Combining Native Mass Spectrometry and Proteomics to Differentiate and Map the Metalloform Landscape in Metallothioneins.

Within the intricate landscape of the proteome, approximately 30% of all proteins bind metal ions. This repertoire is even larger when considering all the different forms of a protein, known as proteoforms. Here, we propose the term "metalloforms" to refer to different structural or functional variations of a protein resulting from the binding of various hetero- or homogeneous metal ions. Using human Cu(I)/Zn(II)-metallothionein-3 as a representative model, we developed a chemical proteomics strategy to simultaneously differentiate and map Zn(II) and Cu(I) metal binding sites. In the first labeling step, N-ethylmaleimide reacts with Cysteine (Cys), resulting in the dissociation of all Zn(II) ions while Cu(I) remains bound to the protein. In the second labeling step, iodoacetamide is utilized to label Cu(I)-bound Cys residues. Native mass spectrometry (MS) was used to determine the metal/labeling protein stoichiometries, while bottom-up/top-down MS was used to map the Cys-labeled residues. Next, we used a developed methodology to interrogate an isolated rabbit liver metallothionein fraction containing three metallothionein-2 isoforms and multiple Cd(II)/Zn(II) metalloforms. The approach detailed in this study thus holds the potential to decode the metalloproteoform diversity within other proteins.

The Hydrogen Evolution Reaction: Using Molecular Design in Transition Metal Complexes to Control Catalytic Microenvironments on Electrode Surfaces

AbstractHydrogen gas and its production from renewable power sources will be an important part of decreasing global reliance on fossil fuels and developing a sustainable energy economy. Efficient electrocatalysis, however, relies on the delivery of both protons and electrons; ideally in a concerted fashion to avoid high energy intermediates, prevent charge build‐up, and circumvent large kinetic barriers. While this can be achieved using ligand design in homogenous molecular transition metal catalysts (specifically incorporating proton shuttles in the secondary coordination sphere), heterogeneous systems are more desirable from an industrial perspective due to their ease of use and enhanced durability. Supporting transition metal catalysts on electrode surfaces is therefore a promising approach for developing next generation electrocatalysts that retain molecular level control in interfacial environments. This review will first cover key design principles from natural systems, such as hydrogenase enzymes, and then survey some representative examples of synthetic homogeneous hydrogen evolution electrocatalysts that incorporate these important features. We will then discuss transition metal species that have been supported on electrode materials, with a focus on recent advances in the field, and the major challenges that remain.