Metal Loading Research Articles

Trimetallic-doped carbon nitride achieves chondroitin sulfate degradation via a free radical degradation strategy

Traditional Fenton principles for degrading polysaccharides, including chondroitin sulfate (CS), are fraught with limitations, such as strict pH-dependence, higher temperature requirements, desulfurization, and environmentally perilous. In this study, an effective Fenton-like system comprising trimetallic-doped carbon nitride material (tri-CN) with hydrogen-bonded melamine-cyanuric acid (MCA) supramolecular aggregates as its basic skeleton was engineered to overcome the challenges of traditional methods. Detailed material characterizations revealed that, compared to monometallic-doped or bimetallic-doped counterparts, tri-CN offered a larger surface area, higher porosity, and increased metal loading, thereby enhancing reactant accessibility and polysaccharide degradation efficiency. The characterization and activity assessment of the degraded polysaccharide revealed structurally intact products without significant desulfurization, indicating the effectiveness of the designed approach. Moreover, the degraded chondroitin sulfate CS3 catalyzed by tri-CN, exhibited promising antioxidant activity and anti-CRISPR potential. The results elucidated that the high-valent iron species in the material served as primary active sites, catalyzing the cleavage of hydrogen peroxide to generate hydroxyl radicals that subsequently attacked CS chains, leading to their fragmentation. Hence, the designed material can be efficiently applied to polysaccharide degradation, but not limited to photocatalysis, electrocatalysis, sensor, energy storage materials, and wastewater treatment.

Metal–Organic Frameworks Derived Carbon‐Supported Metal Electrocatalysts for Energy‐Related Reduction Reactions

AbstractElectrochemical reduction reactions, as cathodic processes in many energy‐related devices, significantly impact the overall efficiency determined mainly by the performance of electrocatalysts. Metal–organic frameworks (MOFs) derived carbon‐supported metal materials have become one of star electrocatalysts due to their tunable structure and composition through ligand design and metal screening. However, for different electroreduction reactions, the required active metal species vary in phase component, electronic state, and catalytic center configuration, hence requiring effective customization. From this perspective, this review comprehensively analyzes the structural design principles, metal loading strategies, practical electroreduction performance, and complex catalytic mechanisms, thereby providing insights and guidance for the future rational design of such electroreduction catalysts.

Mechanistic study of transition metal loaded/doped Ni − MgO catalyzed dry reforming of methane: DFT calculations

In the context of carbon peaking and carbon neutrality goals, dry reforming of methane (DRM) offers both environmental and economic benefits and holds great promise for development. In this work, based on Ni loaded MgO, two structural models constructed by transition metal loading (TM+Ni − MgO, TM=Fe, Zr, Mo) and doping (Ni − TM/MgO) were used for DRM by density functional theory (DFT). And the adsorption of CO2 and CH4 on these structures was analyzed. The partial density of states (PDOS) and charge density difference (CDD) indicate that due to the presence of unfilled electron d − orbitals in the TM atoms, electron transfer occurs between them and the p − orbitals of the C and O atoms. It facilitates the interactions and enhances the adsorption between CO2 and MgO. On this basis, the DRM reactions on Fe and Ni loaded MgO (FeNi − MgO) and Ni − loaded, Fe − doped MgO (Ni − Fe/MgO) were screened for focused research. It was revealed that the addition of Fe lowered the energy barrier values for some of the elementary reaction steps, allowing the reaction to proceed more easily. And Ni − Fe/MgO showed greater advantages by possessing more stable energy barrier fluctuation intervals (ER1 − ER3) and the smallest CO2 dissociation energy barrier.

Influence of different metal-modified Beta zeolites on the liquid-phase isomerisation of xylene and reaction mechanisms

PX is a very important chemical raw material. There are few studies on the liquid-phase isomerisation of xylene. Here, a series of Beta catalysts with different metal modifications were prepared and tested for many characterisations. The reaction performance of the catalysts was evaluated in the liquid-phase MX isomerisation reaction. The results show that the loading of La, Ce, Mo,Fe and Mg metals decreases the specific surface area and acid content of Beta zeolite. Among them, Mo has a strong interaction with the skeleton Al atoms in Beta. The side reactions of MX isomerisation were inhibited by metal loading, and the selectivity of PX and OX was improved. The effect of Mo content on the liquid-phase isomerisation of MX was further investigated. The selectivity of PX can be improved by appropriate Mo content. This is related to the reaction mechanism of the liquid-phase isomerisation of MX at mainly low temperatures. The acidic site density of B and L acids on the catalyst surface was successfully modulated by Mo loading. At 260 °C, the conversion of MX over Mo/Beta catalyst was about 33 % and the PX yield was 12.83 %. In addition, based on the results of liquid-phase isomerisation of MX, OX and PX, the transformation relationship between the three isomers was investigated.

Efficient Electrochemical Reduction through Flow Cells Using Spherical-Polymer Based Carbon Supported Catalysts as Fixed-Bed Electrode

The transition to economically friendly feedstocks and the electrification of chemical synthesis reactions gained much attention in the recent years. To be able to compete with the conventional processes, it is crucial not only to concentrate on the electrochemical reactions itself but also to constantly improve the reactor concepts. A vast variety of designs are imaginable and already well-described – from a simple, undivided beaker cell setup to a divided flow cell with separate electrolytes at cathode and anode. [1] As electrode material not only flat metal electrodes are studied, but also the concept of using carbon supported metal nanoparticles is well-known to employ high dispersion to lower the total amount of required metal. [2,3] While there are already commercial flow reactors and electrodes available for electrosynthesis with flat standard electrodes, reactors using a fixed-bed of porous carbon with nanodispersed metals as electrode just recently started to attract attention. [4] Dealing with the pressure drop over the catalyst bed, while the electrical contact is still ensured, are key challenges for this reactor design. Spherical polymer-based carbons (SPBC) combine porous carbons properties with a high purity and especially spherical character. [5] While these advantages led already to commercial products for chromatographic applications (e.g. Carboxen®) the potential regarding flow-electrochemistry has not been leveraged. Key developments for this are reproducible synthesis procedures to deposit active metal on the SPBCs and the design of an electrochemical flow cell using these catalysts in a fixed-bed electrode configuration.The first part of this work presents the deposition of Cu through different impregnation and reduction procedures on a SPBC (Carboxen® 1032, 50 µm, Merck). The carbon was characterized by physisorption, TPD-MS, TPO, Raman and SEM. The resulting metal-impregnated carbon catalysts were additionally investigated regarding the metal loading. Using the applied impregnation and reduction parameters targeted metal loadings (3 – 20 wt%) could be well achieved. The second part focuses on the design and commissioning of a flow-cell for the application of the SPBC-supported catalysts as a fixed-bed at the cathode side. Electrochemical synthesis reactions are targeted in the cell and the reduction of 5-HMF to BHMF was chosen as the test reaction in this work. In the framework of the cell development multiple aspects not only regarding the construction but also reaction engineering issues had to be considered: material stability of the pump, fixation and pressure drop of catalyst bed, choice of electrolyte, effect of dissolved oxygen in the catholyte, optimal flow rate, reliable electrochemical protocol and selection of contact material. The latter has to be a compromise between chemical inertness and an enhanced electron transfer between the catalyst bed and the contact material (e.g. soft foil vs. hard metal). Figure 1A shows the current voltage characteristics of two possible contact materials (graphite foil, boron-doped diamond (BDD)) in the targeted electrolyte (0.5M borate buffer with 0.25M potassium chloride). Here, the graphite foil clearly shows a higher activity towards the hydrogen evolution reaction which may result in a less effective electrolysis later on. The comparison of BDD as contact material without and with a catalyst bed (Carboxen® 1032 loaded with 20 wt% Cu) resulted in a significant shift in the current voltage characteristic to lower overpotentials. Therefore, the electronic contact with the carbon bed is clearly enabled and the carbon spheres loaded with copper catalyze the reaction. Figure 1B presents the results of the test reaction with the conversion of the educt 5-HMF as well as the selectivity to the targeted product BHMF over the reaction time with BDD as contact material without and with a fixed bed of Cu/SPBC catalyst. The experiments prove full 5-HMF conversion within 23 h on stream in combination with a high selectivity towards BHMF with the catalyst bed. The mass-based productivity reaches values of up to 1.78 mmol h-1 gCu -1 and is therefore about 15 times higher compared to the use of conventional Cu foil (Pliterature = 0.11 mmol h-1 gCu -1 [6]). It is possible that due to the metal-support approach in the fixed-bed configuration, the copper is leveraged more efficiently and small amounts allow to provide sufficient metal surface area for the catalytic reaction.

Introducing Platinum Cryoaerogel As a Low Loading Cathode Catalyst in PEM Water Electrolysis

An important cost factor for polymer electrolyte membrane water electrolysers is precious metals as the catalyst layers. Therefore, reducing of the platinum loading on the cathode side and the iridium on the anode is essential to reduce the overall costs of hydrogen production. Cryoaerogels from noble metal nanoparticles are a suitable, yet unexplored material for use as a catalyst in water electrolysis. They combine high porosity and surface area with an excellent catalytic activity at low loadings of noble metal.[1] Recently, we have succeeded in producing a carbon-based gas diffusion electrode (GDE) coated with platinum cryoaerogel as the catalyst. The mechanical connection to the carbon underneath as well as maintaining a high protonic conductivity in contact to the Nafion membrane allowed the application to the water electrolysis cell. The manufacturing includes an oven treatment, whose temperature is particularly decisive for the structure of the cryoaerogel. Figure 1 left shows the polarization curves of the samples pyrolyzed at 300°C, 350°C and 500°C compared to a commercial GDE (platinum loading of 0.5 mg/cm²). All measurements are repeated three times and showed good reproducibility, as indicated by the error bars on the graph. Among the different temperatures, 300°C is the optimum for the pyrolysis process as it showed the lowest voltages. The catalytic performance of the different samples can be correlated to the micro-structure of the cryoaerogel layer represented by the SEM images and the electronic-structure of the platinum as shown by X-ray photoelectron spectroscopy (XPS). Although in figure 1 the performance of the cryoaerogel catalyst layers is not better than the commercial GDE, however, the platinum loading is significantly reduced by 70% (0.15 mg/cm2). Moreover, the reproducibility of the measurements proofs the possibility of using cryoaerogels in the full water electrolysis cell.[1] Müller, D., Zámbó, D., Dorfs, D., Bigall, N. C., Cryoaerogels and Cryohydrogels as Efficient Electrocatalysts. Small 2021, 17, 2007908. https://doi.org/10.1002/smll.202007908 Figure 1

Distinguishing Electrochemical Processes in PEM Electrolysis By Impedance Modeling – Distribution of Relaxation Times

Proton exchange membrane (PEM) water electrolysis is a key technology in hydrogen production to provide capacity and flexibility for renewable energy power sources. Various research topics for electrolyzer development focus on cost reduction, performance optimization and lifetime extension with minimum platinum group metal (PGM) loading required [1]. Understanding degradation mechanisms in PEM electrolysis cells becomes necessary for developing mitigation strategies in dynamic durability tests, which facilitates the importance of advanced electrochemical characterization methods.Electrochemical impedance spectroscopy (EIS) is a commonly used diagnostic technique in electrochemical systems. For impedance interpretation, equivalent circuit model (ECM) can be an option with prior knowledge about the system and appropriate circuit elements to prevent overfitting. Alternatively, distribution of relaxation times (DRT) provides a model-free pathway to address electrochemical mechanisms with different time constants and it has been applied to fuel cells, batteries and capacitors in the past years [2, 3]. Impedance deconvolution by DRT, however, has not been well adapted for PEMECs. In this study, electrochemical processes are successfully identified from the DRT profile by varying membrane electrode assembly (MEA) compositions and different operational conditions. In a single cell testing, four main peaks in DRT results associated with (1) mass transport losses (2) reaction kinetic (3) ionic conductivity within the catalyst layer and (4) ohmic properties at the interface of membrane and catalyst layers can be separated and quantified. Examination of electron microscopy provides further explanation of different MEA characteristics in performance analysis. This study verifies DRT is a promising tool to better understand PEM electrolysis processes and will be applied to degradation mitigation in the future.

Approaching the Multiphase Interface of Ir-Based PEM Electrolyzers Using Operando ‘Tender’ X-Ray AP-XPS

Electrochemical water splitting is a promising pathway for the renewable production of hydrogen as an alternative fuel and chemical feedstock. Yet, the process is plagued by slow kinetics of the essential oxygen evolution reaction at the anode. Further, large-scale hydrogen production from such devices will require reduced platinum group metal (PGM) loadings (often iridium-based anodes) and/or new materials due to factors such as PGM scarcity, cost and loss during operation. In the hopes of enabling progress of rational design for OER catalysts, effective characterization of the electrode-liquid interface is crucial. Synchrotron-based X-ray Photoelectron Spectroscopy (XPS) offers a versatile way to obtain surface chemical and elemental characterization of these materials. The use of X-rays in the ‘tender’ regime (~2-6 keV) allows for deeper probing than the conventional ‘soft’ x-ray (< 2000 eV) set up that is common at synchrotrons and lab-based sources. The photoelectrons generated from tender x-rays have enough energy to penetrate tens of nanometers through low density components such as a layer of liquid or polymeric electrolyte. This opens the door to access the chemistry at the interface of liquid and ionomer electrolyte-electrocatalyst materials. With the use of a fully operational two-electrode system, we are able to study these membrane electrode assemblies under active water splitting conditions.My talk will explain our specific approach, which is often crucial for successful collection of accurate data, highlighting elements of cell design and experimental setup that are helpful for this process. I will also show recent AP-XPS results on iridium-based polymer electrolyte membranes for water splitting. With application of elevated potential, we can correlate the iridium valency and surface species with the appearance of product traces in a mass spectrum. Figure 1

(Invited) Novel Design of Low-Loaded Membrane Electrode Assemblies for Advanced Low-Temperature Water Electrolyzers

Development of advanced low-temperature (LT) water electrolyzers (WEs) is of crucial importance for implementation of the Hydrogen Economy. This future green economy will eliminate the greenhouse gas emissions and stop the imminent global warming and climate change. “Green” hydrogen can be produced at large scale by integration of WEs with renewable energy sources. Currently, the low-temperature proton exchange membrane (PEM) and anion exchange membrane (AEM) WEs are considered to be the most advanced WEs that can be integrated with solar panels and wind turbines to produce large quantities of green H2. The main challenges that the state-of-the-art membrane electrode assemblies (MEAs) for LTWEs are currently facing are: (i) high cost because of the high platinum group metals (PGM) loadings in their catalysts layers; (ii) limited durability caused by the instability of the catalysts and the other cell components, and (iii) safety concerns associated with the hydrogen gas crossover and the absence of technologies that can effectively keep it below the safety level of the lower flammability limit (LFL) [1, 2, 3].This work is aimed on designing of novel MEAs for LTWEs with dramatically reduced catalysts loadings, enhanced durability, and improved H2 crossover capabilities. Reactive Spray Deposition Technology (RSDT) is used as an innovative methodology for designing of advanced catalysts, catalyst and recombination layers, and MEAs for LTWEs. The RSDT is a flame assisted method [4, 5] that combines the catalysts synthesis and deposition directly on the membrane in one-step, which results in fast and facile fabrication of large scale (up to 1000 cm2) MEAs for application in LT fuel cells and water electrolyzers [5, 6]. As fabricated MEAs with ultra-low PGM catalysts loadings are tested at operating conditions typical for industrial PEM hydrogen production systems, and performance of 1.8 V at 3 A/cm2 is achieved. The MEAs of interest are tested for over 1000 hrs at steady-state conditions at 3 A/cm2. Comprehensive post-test characterization is performed by using high-resolution TEM, STEM, EDS, SEM, ICP, XRF, XCT, and digital optical microscopy and the governing degradation mechanisms are identified and discussed in detail. The impact of the design of low-loaded MEAs for LTWEs on their performance and durability is discussed in detail and their potential to meet and surpass the DOE 2030 targets is demonstrated.References https://www.energy.gov/sites/prod/files/2017/05/f34/fcto_myrdd_fuel_cells.pdf https://www.energy.gov/sites/prod/files/2015/06/f23/fcto_myrdd_production.pdfKlose, P. Trinke, T. Böhm, B. Bensmann, S. Vierrath, R. Hanke-Rauschenbach, and S. Thiele, J. Electrochem. Soc., 165, F1271–F1277 (2018).Kim, S., Myles, Maric, R., et al. Electrochimica Acta, 177, 190-200 (2015).Yu, H., Baricci, A., Bisello, A., Bonville, L., Maric, R., et al. Electrochimica Acta, 247, 1155-1168 (2017).Mirshekari, G., Ouimet, R., Zeng, Z, Yu, H., Bliznakov, S., Bonville, L., Niedzwiecki, A., Errico, S., Capuano, C., Mani, P., Ayers, K., Maric, R. International Journal for Hydrogen Energy, 46(2), 2021, pp. 1526-1539 (2021).

Advanced Porous Transport Electrode for High-Performance Proton Exchange Membrane Water Electrolyzers

Proton exchange membrane water electrolyzers (PEMWEs) hold great potential for supplying green hydrogen to support extensive energy storage and mobility in a future energy landscape centered on renewable energy sources.1,2 However, their contribution to global hydrogen production is currently limited, mainly due to their comparatively high cost.3 To improve the economic competitiveness of green hydrogen and foster broader market penetration, the Department of Energy (DOE) has launched the Hydrogen Earthshots, aiming for a substantial cost reduction to $2 per kilogram by 2025 and $1 per kilogram for green hydrogen by 2030.4 The high efficiency and prolonged durability are pivotal for the overall performance and cost reduction of the PEMWEs. This requires careful consideration of the interfacial contact between the porous transport layer (PTL) and the anode catalyst layer.5 One option for PEMWEs is to directly coat the anode catalyst layer onto the PTL, forming porous transport electrodes (PTEs). Recent literature suggests that it is feasible to manufacture PTEs with low precious metal loading, demonstrating both high performance and durability.6,7 In this study, an innovative reactive spray deposition technology (RSDT) is used to fabricate PTEs with low PGM loading (0.2 - 0.3 mgPGM cm-2) in both catalyst layers. The RSDT is a flame-based method that combines the synthesis and deposition of the catalyst in a single step, significantly reducing the fabrication time and cost of the membrane electrode assembly (MEA).8–11 The RSDT-fabricated PTEs are coupled with various membranes, and their performance has been assessed and compared to the state-of-the-art MEAs for PEMWEs. In addition, the performance loss in each cell has been studied and discussed in detail. Furthermore, a standard accelerated stress test (AST) protocol has been applied to assess the durability of the RSDT-fabricated MEAs, with one order of magnitude lower PGM loading in their catalyst layers in comparison to the commercial MEAs for PEMWEs.Reference1. Pham, C. Van, Escalera-López, D., Mayrhofer, K., Cherevko, S. & Thiele, S. Essentials of High Performance Water Electrolyzers – From Catalyst Layer Materials to Electrode Engineering. Adv. Energy Mater. 11, (2021).2. Carmo, M., Fritz, D. L., Mergel, J. & Stolten, D. A comprehensive review on PEM water electrolysis. Int. J. Hydrogen Energy 38, 4901–4934 (2013).3. Buttler, A. & Spliethoff, H. Current status of water electrolysis for energy storage, grid balancing, and sector coupling via power-to-gas and power-to-liquids: A review. Renew. Sustain. Energy Rev. 82, 2440–2454 (2018).4. Styapal, S. et al. DOE Update on Hydrogen Shot, RFI Results, and Summary of Hydrogen Provisions. (2021).5. Peng, X. et al. Insights into Interfacial and Bulk Transport Phenomena Affecting Proton Exchange Membrane Water Electrolyzer Performance at Ultra-Low Iridium Loadings. Adv. Sci. 8, (2021).6. Xie, Z. et al. Ionomer-free nanoporous iridium nanosheet electrodes with boosted performance and catalyst utilization for high-efficiency water electrolyzers. Appl. Catal. B Environ. 341, 123298 (2024).7. Lee, J. K. et al. Ionomer-free and recyclable porous-transport electrode for high-performing proton-exchange-membrane water electrolysis. Nat. Commun. 14, 1–11 (2023).8. Zeng, Z. et al. Advanced nickel-based catalysts for the hydrogen oxidation reaction in alkaline media synthesized by reactive spray deposition technology: Study of the effect of particle size. Int. J. Hydrogen Energy 1–12 (2023) doi:10.1016/j.ijhydene.2023.03.249.9. Zeng, Z. et al. Degradation Mechanisms in Advanced MEAs for PEM Water Electrolyzers Fabricated by Reactive Spray Deposition Technology. J. Electrochem. Soc. 169, 054536 (2022).10. Xing, J. et al. Long-term durability test of highly efficient membrane electrode assemblies for anion exchange membrane seawater electrolyzers. J. Power Sources 558, 232564 (2023).11. Mirshekari, G. et al. High-performance and cost-effective membrane electrode assemblies for advanced proton exchange membrane water electrolyzers: Long-term durability assessment. Int. J. Hydrogen Energy 46, 1526–1539 (2021).

Limiting Current Density in Water Vapor-Fed Polymer Electrolyte Membrane Electrolyzers

Polymer electrolyte membrane water electrolyzers (PEMWE) are a critical technology in development for addressing the need for efficient hydrogen production. In order to make hydrogen a cost-effective fuel or industrial feedstock, the overpotentials across the cell needs to be decreased and platinum-group metal loading reduced. Devising novel electrode structures that enable ultra-high current densities at low oxygen evolution reaction (OER) catalyst (e.g. Iridium oxide) loadings is one approach to achieving efficiency and cost targets. One of the overpotentials that needs to be addressed is due to mass transport limitations within the porous transport layer (PTL) and anode catalyst layer, which could be a limiting factor at ultra-high current densities. When operating at ultra-high current densities, the rate of the OER may reach a point at which oxygen gas bubbles fill the pores of the anode catalyst layer PTL, blocking access of liquid water to the anode catalyst layer. Because of this, there is a possibility that the cell will rely on water vapor diffusion through the evolving oxygen gas to deliver the water reactant to the OER catalyst. To assess the limitation of a PEMWE while relying on water vapor diffusion, a commercially manufactured membrane electrode assembly (MEA) was tested by flowing water vapor into the anode as the reactant. With the aim of identifying a limiting current density (LCD) of the electrolyzer under these conditions, potentiostatic polarization curves were obtained for a range of relative humidities (RH) and back pressures. The RH was varied to assess the impact of reactant concentration on the LCD, while the back pressure was varied to identify the impact of the molecular gas diffusion coefficient on the LCD. In this presentation, we will present our analysis of the significance of the water vapor diffusion transport resistance through the pressure-dependent resistance evaluation. Furthermore, we will discuss application of this approach to evaluating the impact of vapor operation on membrane water transport and OER reaction kinetics.

In-situ preparation of MnFeCoNiCu/C for the sustainable co-production of bio-jet fuel and green diesel under solvent-free and low hydrogen pressure conditions

The conversion of non-edible oils such as fatty acid methyl esters (FAME) into green and renewable liquid fuels align with the current trend of sustainable development. However, traditional processes often involve multi-step process to prepare catalyst and require high-pressure hydrogen. This study reports a strategy for the in-situ preparation of MnFeCoNiCu/C catalyst, enabling the one-step conversion of FAME into bio-jet fuels and hydrocarbon-based diesel under solvent-free and low-pressure conditions. The effect of active metal loading, reaction temperature, hydrogen pressure, and ZSM-5 zeolite addition on the catalytic performance was investigated. Under the conditions of reaction temperature 350 ℃ and hydrogen pressure 2 MPa, the conversion rate of FAME reaches 100 %, and the selectivity of bio-jet fuel and green diesel is 48.35 % and 51.05 %, respectively. A small number of olefins, cycloalkanes, and aromatics can also be detected in the products. After the 4 cycles of AC-15 catalyst, the selectivity of bio-jet fuel and diesel are 40.09 % and 39.81 %, respectively. The above research work provides a mild and efficient method for the preparation of renewable bio-jet fuel and green diesel.

Chromium-extracted aluminum catalyst for co-pyrolysis of cotton fabric waste and polypropylene plastic waste to bio-oil

Heterogeneous catalysts of chromium-extracted aluminum (CE) were prepared and used to produce bio-oil from the co-pyrolysis of cotton fabric waste (CFW) and polypropylene waste (PPW). The catalysts were synthesized via wet impregnation at 5–20 wt% catalyst loading and calcined at 600 °C for 5 h. The co-pyrolysis was conducted in a fixed-bed reactor at 500 °C for 1 h with 1:1 CWF/PPW ratio and 1:1 catalyst/feedstock ratio. The physical and chemical properties of the catalysts and bio-oil were characterized by several techniques such as Brunauer–Emmet–Teller, scanning electron microscopy, energy dispersive x-ray spectroscopy, x-ray diffraction, temperature-programmed desorption and gas chromatography-mass spectrometry. Investigations into the effects of metal loadings revealed that the 15CE catalyst was the most active, achieving a maximum bio-oil yield of 76.4 % and producing valuable chemical compounds like hydrocarbons, alcohols, phenols, and furans. The XRD of 15CE catalyst confirmed the presence of chromium oxide and assigned to the rhombohedral phase of the crystal lattice. BET indicated 15CE has the largest surface area (50.4 m2/g) among the CE catalysts which contributed to its high activity. The SEM revealed CE catalysts at different metal loadings contain irregular shapes and sizes with a rough surface texture. The NH3-TPD profiles indicated alterations in acid site distribution due to the interaction between the introduced Cr metal and EA. The 15CE catalyst also demonstrated significant reusability, maintaining performance after two regeneration cycles. These results confirm the potential of CE catalysts in enhancing bio-oil production from CFW and PPW.

Ammonia-regulated dynamic evolution of Ti precursor incorporating into dealuminized beta for efficient 1-Hexene epoxidation

Demetalation-metalation method has gained prominence for its higher metal loading, efficiency and shortened synthetic period, particularly in the incorporation of metal atoms with large radii into zeolite framework in recent years. An ammonia-regulated approach has been developed for selectively evolved deep-substituted Ti precursors in dealuminized beta zeolites, which enables a controlled promotion of metalation of Ti atoms. Additionally, this ammonia-regulated approach could also enhance 1-hexene kinetic adsorption by constructing mesopores, which is demonstrated by the lower reaction order of 1-hexene. The synthesized ammonia-regulated N-Ti-beta exhibits rich framework Ti species and a high specific surface area, leading to significantly improved 1-hexene epoxidation performance (conversion of 61%, selectivity of 98%, and a high H2O2 utilization efficiency of 93%). This study not only provides a new strategy to dynamically regulate evolution of Ti precursors by ammonia but also holds promise for advancing related industrial processes in demetalation-metalation methods.

Pronounced declines in heavy metal burdens of Minnesotan mammals over the last century

Humans have drastically altered the ecology of heavy metals, which can have negative effects on animal development and neural functioning. Many species have shown the ability to adapt to anthropogenic increases in metal pollution, but such evolutionary responses will depend on the extent of metal variation over space and time. For terrestrial vertebrates, it is unclear how metal exposure has changed over time: some studies suggest metal content peaked with the enactment of policies controlling lead emissions, while other studies suggest metal levels peaked at least a century earlier. We used 162 specimens of four mammal species (a mouse, shrew, bat, and squirrel) to ask how metal content of the fur and skin has changed over a 90-year time period, and impacts on individual performance (body size and cranial capacity). Using ICP-MS, we show that for lead, cadmium, copper, and chromium, there were significant declines in metal content in mammal tissue over the 90-year time period, with lead levels five times lower now than in the early 1900s. Importantly, metal content began to drop well before the pollution regulation of the 1970s. Effects of time greatly outweighed any effects of an individual living near a human population center. Surprisingly, there were no effects of body metal content on body size, and only manganese was negatively related to relative cranial capacity. Taken together, these results suggest that present day populations of mammals are experiencing levels of heavy metal exposure that are less stressful than they were 100 years ago. In addition, temporal decreases in metal loads likely partly reflect global patterns of pollution decline that affect atmospheric metal deposition rather than local point sources of exposure.

Assessment of heavy metal contamination risk in dry fish from India: A comprehensive study

The widespread presence of heavy metal contaminants in aquatic ecosystems, and consequently in fish, has emerged as a paramount concern owing to the staple role of fish in the Indian diet. The present study addresses heavy metal contamination in dried fish consumed across India and its associated health risks. The objectives of this study were to determine the heavy metal concentrations in dried fish from different regions of India, assess daily heavy metal intake through dried fish consumption, and evaluate the carcinogenic and non-carcinogenic health risks associated with heavy metal exposure. Subsequently, 111 dried fish samples from Guwahati-Assam, Mumbai, Karad-Maharashtra, and Goa were analyzed for eight selected heavy metals using a validated inductively coupled plasma mass spectrometry method results indicated varying contamination levels across locations, with As being the most abundant heavy metal. In Maharashtra and Assam, the heavy metal load in dried fish was as follows: As > Cr > Ni > V > Cd > Pb > Co > Hg. For Goa, the order was As > Cr > Ni > V > Cd > Co > Pb > Hg. Dietary exposure assessments revealed varying levels of exposure between adults and children, with As and Cd posing higher risks to children. The Target Hazard Quotient (THQ) and Hazard Index (HI) values for all metals were within acceptable limit of one. Health risk assessments revealed generally low hazard levels for adults, but higher risks for children, particularly at higher percentiles. Furthermore, As was identified as posing a medium risk of cancer. In essence, this research emphasizes the necessity for strict monitoring and regulations with the aim of controlling health hazards related to heavy metal pollution in food sources.

Utilization of coal gasification fine slag-derived mesoporous silica supports for enhanced dry reforming of methane catalysts

Utilizing industrial waste coal gasification fine slag (CGFS) for the preparation of dry reforming of methane (DRM) catalyst supports presents an innovative approach to waste utilization. This strategy not only addresses solid waste pollution but also reduces the production costs associated with DRM catalysts. Currently, the industrialization of the DRM reaction remains elusive. Therefore, selecting an appropriate catalyst preparation method is imperative for potential industrial applications. This study centers on the synthesis of mesoporous silica (MS) supports using coal gasification fine slag. The impact of support structure, catalyst preparation method, and active metal loading on the resistance to sintering and carbon deposition of the catalysts is explored through diverse characterization techniques. The MS support derived from coal gasification fine slag showcases a unique disordered mesoporous architecture that enhances the dispersion of the metal across the support surface. In addition, we report a MS catalyst prepared by a co-precipitation method (MS–CP), which exhibits excellent catalytic activity and stability due to its strong metal-support interaction. Results suggest that during synthesis, the MS–CP catalyst activates the inert MS support by strongly interacting with Ni metal, resulting in the formation of Ni3Si2O5(OH)4 species. The Ni–O–Si bond can activate CO2, thereby promoting the availability of interfacial oxygen during the reaction. This process accelerates the gasification of surface Cn generated by CH4 decomposition. Notably, the loading analysis indicates that MS–CP loaded with 10 wt% Ni demonstrates the highest resistance to carbon deposition and sintering. Thus, the unique strong metal-supported interactions provide a new avenue for the development of nickel-based DRM catalysts.

ZnO nanowires decorated with Pt nanoclusters for selective detection of ppb-level nitrogen dioxide

Noble metal loading is an efficient way to improve the sensing performance of metal oxide semiconductor (MOS) gas sensors. In this work, platinum (Pt) nanoclusters loaded ZnO nanowires (Ptc-ZnO) were used to fabricate a NO2 sensor. Pure ZnO nanowires were prepared by a solvothermal method and Pt nanoclusters were loaded via a sacrificial templating route. The Ptc-ZnO based sensor with a trace of Pt loading (0.17 wt%) shows a high response to ppb-level NO2 (26.1–100 ppb), 4.4 times higher than that of pure ZnO. Additionally, it also exhibits excellent selectivity, low theoretical limit of detection (1.19 ppb) and good stability to humidity. The enhancing mechanism on gas sensing performance by Pt loading was discussed and investigated via HAADF-STEM, XPS, NO2-TPD and other methods. This work provides a way to develop gas sensor for ultralow NO2 concentration real-time detection.

Potential contamination of groundwater quality in west Algeria by non-biodegradable effluents from public discharges

The aim of this work is to study the environmental impact of the municipal landfill in the town of Sidi Bel Abbes (western Algeria), in particular on the water table, which circulates at a shallow depth (Max. 20 m) under permeable soil. The huge quantities of putrescible waste discharged into this landfill generate highly polluting leachate water, rich in organic matter (COD up to 1300 mg/L, 209 mg/L in BOD5), salts and micro-organisms. A physico-chemical study of well water in the region reveals a significant deterioration in the quality of the underlying groundwater. In fact, electrical conductivities (on average 5.75 mS/cm) are common in wells, especially those located close to the landfill site. This indicates heavy contamination of the water in these wells by leachate. As for the organic and metallic load, abnormally high levels (82 mg/l in COD, 40 mg/l in BOD₅, 0.74 mg/L in Cr, 0.45 mg/L in Cd, 0.24 mg/L in Cu, 0.85 mg/L in Ni) were observed, mainly in the wells located near and downstream of the landfill, in the direction of groundwater flow.

Engineering Single‐Atom Catalysts on Conjugated Porphyrin Polymer Photocatalysts via E‐Waste for Sustainable Photocatalysis

AbstractThis study presents a surface engineering strategy utilizing electronic waste (e‐waste) to incorporate single‐atom catalysts on conjugated polymers. Employing a conjugated porphyrin polymeric photocatalyst, gold single‐atom‐site catalysts are successfully introduced using the acidic metal leachates from e‐waste, where metal speciation and composition are regulated during the metal loading processes. The resulting photocatalyst with gold single atoms demonstrates a remarkable hydrogen peroxide (H2O2) selectivity of up to 97.56%, yielding a pure H2O2 solution at 73.3 µm h−1 under white LED illumination. The produced H2O2 is activated to •OH radicals on the same polymer with mixed gold and iron atoms, enabling a photo‐Fenton reaction and the complete degradation of toxic microcystin‐LR within 10 min under visible light. This study highlights the universal applicability of the metal mining strategy in various photoreactions. It is believed that this discovery pioneers sustainable photocatalysis, allowing the tuning of reactivity and selectivity on photocatalytic surfaces using metal waste.