Search Results (652)

Polymyxin antibiotics are often the last line of defense against multidrug-resistant Gram-negative pathogens. A key resistance mechanism involves the addition of 4-amino-4-deoxy-L-arabinose (L-Ara4N) to lipid A, mediated by the bifunctional enzyme ArnA. However, the evolutionary rationale and structural basis for ArnA’s domain fusion, hexameric assembly, and catalytic coordination remain mechanistically unresolved. Here, we integrate evolutionary genomics, high-resolution cryo-electron microscopy (cryo-EM), and computational protein design to provide a comprehensive mechanistic analysis of ArnA. Our evolutionary analysis reveals that the dehydrogenase (DH) and formyltransferase (TF) domains evolved independently and were selectively fused in Gammaproteobacteria, suggesting an adaptive advantage. A 2.89 Å cryo-EM structure of apo-ArnA resolves the flexible interdomain linker and reveals a DH-driven hexameric architecture essential for enzymatic activity. 3D variability analysis captures intrinsic conformational dynamics, indicating a molecular switch that may coordinate sequential catalysis and substrate channeling. Structure-based peptide inhibitors targeting the hexamerization and predicted ArnA–ArnB interaction interfaces were computationally designed, offering a novel strategy for disrupting L-Ara4N biosynthesis. These findings illuminate a previously uncharacterized structural mechanism of antimicrobial resistance and lay the groundwork for therapeutic intervention. Full article

Mercury (Hg) contamination in water and soil poses severe ecological and human health risks, yet conventional sorbents often suffer from limited capacity, selectivity, and stability. Here, we report a bifunctional porous organic polymer (AMTD-TCT) rationally constructed by covalently crosslinking 2-amino-5-mercapto-1,3,4-thiadiazole with trichlorotriazine, thereby integrating abundant sulfur and nitrogen coordination sites within a stable mesoporous framework. AMTD-TCT exhibits an ultrahigh Hg(II) adsorption capacity of 1257.7 mg g⁻¹, far exceeding most reported porous sorbents. Adsorption follows monolayer chemisorption, governed by strong S–Hg and N–Hg coordination and Na⁺/Hg²⁺ ion exchange, while hierarchical porosity ensures rapid diffusion and efficient utilization of active sites. The polymer maintains robust performance over a wide pH range and demonstrates strong retention with minimal desorption, underscoring its environmental durability. These findings highlight AMTD-TCT as a highly effective and scalable platform for Hg(II) remediation in complex aqueous–soil systems and illustrate a generalizable molecular design strategy for developing multifunctional porous polymers in advanced separation and purification technologies. Full article

Electrocatalytic water splitting offers a promising route to sustainable H₂, but the oxygen evolution reaction (OER) in alkaline media remains the principal bottleneck for activity and durability. This review focuses on alkaline OER and integrates mechanism, kinetics, materials design, and cell-level considerations. Reaction mechanisms are outlined, including the adsorbate evolution mechanism (AEM) and the lattice oxygen mediated mechanism (LOM), together with universal scaling constraints and operando reconstruction of precatalysts into active oxyhydroxides. Strategies for electronic tuning, defect creation, and heterointerface design are linked to measurable kinetics, including iR-corrected overpotential, Tafel slope, charge transfer resistance, and electrochemically active surface area (ECSA). Representative catalyst families are critically evaluated, covering Ir and Ru oxides, Ni-, Fe-, and Co-based compounds, carbon-based materials, and heterostructure systems. Electrolyte engineering is discussed, including control of Fe impurities and cation and anion effects, and gas management at current densities of 100–500 mA·cm⁻² and higher. Finally, we outline challenges and directions that include operando discrimination between mechanisms and possible crossover between AEM and LOM, strategies to relax scaling relations using dual sites and interfacial water control, and constant potential modeling with explicit solvation and electric fields to enable efficient, scalable alkaline electrolyzers. Full article

The development of durable and efficient catalysts capable of driving both hydrogen and oxygen evolution reactions is essential for advancing sustainable hydrogen production through overall water electrolysis. In this study, we developed a corrosion-mediated approach, where Ni ions originate from the self-corrosion of the nickel foam (NF) substrate, to construct Pt-modified NiFe layered double hydroxide (Pt-NiFeO_xH_y@NiFe-LDH) under ambient conditions. The obtained catalyst exhibits a hierarchical architecture with abundant defect sites, which favor the uniform distribution of Pt clusters and optimized electronic configuration. The Pt-NiFeO_xH_y@NiFe-LDH catalyst, constructed through the interaction between Pt sites and defective NiFe layered double hydroxide (NiFe-LDH), demonstrates remarkable hydrogen evolution reaction (HER) activity, delivering an overpotential as low as 29 mV at a current density of 10 mA·cm⁻² and exhibiting a small tafel slope of 34.23 mV·dec⁻¹ in 1 M KOH, together with excellent oxygen evolution reaction (OER) performance, requiring only 252 mV to reach 100 mA·cm⁻². Moreover, the catalyst demonstrates outstanding activity and durability in alkaline seawater, maintaining stable operation over long-term tests. The Pt-NiFeO_xH_y@NiFe-LDH electrode, when integrated into a two-electrode system, demonstrates operating voltages as low as 1.42 and 1.51 V for current densities of 10 and 100 mA·cm⁻², respectively, and retains outstanding stability under concentrated alkaline conditions (6 M KOH, 70 °C). Overall, this work establishes a scalable and economically viable pathway toward high-efficiency bifunctional electrocatalysts and deepens the understanding of Pt-LDH interfacial synergy in promoting water-splitting catalysis. Full article

The advancement of overall water-splitting technologies relies on the development of earth-abundant electrocatalysts that efficiently produce H₂ as a chemical fuel while offering high catalytic efficiency, structural robustness, and low-cost synthesis. Therefore, we aim to develop a cost-effective and durable non-noble electrocatalyst for overall water splitting. A straightforward hydrothermal approach was employed to fabricate freestanding polyhedral Co₃O₄ on a microporous Ni foam scaffold, followed by anion-exchange transformation in the presence of Na₂S solution to yield its conductive sulfide analog. The engineered Co₃S₄ electrode delivers remarkable HER activity in 1.0 M KOH, requiring a low overpotential (<100 mV) to drive 10 mA cm⁻², far outperforming its pristine oxide counterpart and even closely benchmarking with a commercial Pt/C catalyst. This exceptional performance is governed by the synergistic effects of enhanced electrical conductivity, abundant catalytic sites, and accelerated charge-transfer kinetics introduced through sulfur substitution. Furthermore, the optimized Co₃S₄ electrodes enable a bifunctional overall water-splitting device that achieves a cell voltage of >1.76 V at 100 mA cm⁻² and maintains prolonged operational stability for over 100 hrs. of continuous operation. Post-stability analyses confirm insignificant phase preservation during testing, ensuring sustained activity throughout the electrolysis process. This study highlights the potential of anion-exchanged Co₃S₄ as a cost-effective and durable catalyst for high-performance HER and full-cell water-splitting applications. Full article

Developing highly efficient and stable electrocatalysts from inexpensive and earth-abundant elements represents a significant advancement in overall water splitting (OWS). This study focuses on the synthesis and evaluation of palladium-modified cobalt–phosphorus (PdCoP) and cobalt–iron–phosphorus (PdCoFeP) coatings for use as electrocatalysts in hydrogen evolution (HER), oxygen evolution (OER) and overall water splitting (OWS) in alkaline media. A facile electroless plating method is adopted to deposit the CoP and CoFeP coatings onto a copper surface (Cu sheet), with sodium hypophosphite (NaH₂PO₂) acting as the reducing agent. Pd crystallites were incorporated on CoP and CoFeP coatings using the galvanic displacement method. This study details morphological characterization (using SEM, EDX, and XRD), as well as electrochemical activity testing, for both HER and OER using linear sweep voltammetry (LSV) at different temperatures. The stability of the catalysts for HER was evaluated using chronoamperometry (CA) and chronopotentiometry (CP). The results show that the Pd-modified CoFeP and CoP catalysts exhibited lower overpotentials of 207 and 227 mV, respectively, for HER and 396 mV for OER at a current density of 10 mA cm⁻² compared to the unmodified CoFeP and CoP catalysts. The innovation achieved in this study lies in combining a facile, low-cost deposition method (electroless plating followed by galvanic displacement) with a novel, highly effective ternary composition (PdCoFeP) that exploits synergistic electronic and morphological effects to achieve superior bifunctional performance for alkaline OWS, achieving a low cell voltage of 1.69 V at a current density of 10 mA cm⁻². Overall, this research demonstrates that these synthesized materials are promising candidates for sustainable and economical hydrogen production. Full article

Biodiesel is an alternative, sustainable, renewable, and environmentally friendly energy source, which has generated interest from the scientific community due to its low toxicity, rapid biodegradability, and zero carbon footprint. Biodiesel is a biofuel produced by the transesterification of triglycerides or the esterification of free fatty acids (FFA). Both reactions require catalysts with numerous active sites (basic, acidic, bifunctional, or enzymatic) for efficient biodiesel production. On the other hand, since the late 1990s, metal–organic frameworks (MOFs) have emerged as a new class of porous materials and have been successfully used in various fields due to their multiple properties. For this reason, MOFs have been used as heterogeneous catalysts or as a platform for designing active sites, thus improving stability and reusability. This literature review presents a comprehensive analysis of using MOFs as heterogeneous catalysts or supports for biodiesel production. The optimal parameters for transesterification/esterification are detailed, such as the alcohol/feedstock molar ratio, catalyst amount, reaction time and temperature, conversion percentage, biodiesel yield, fatty acid and water content, etc. Additionally, novel methodologies such as ultrasound and microwave irradiation for obtaining MOF-based catalysts are described. It is important to note that most studies have shown biodiesel yields >90% and multiple reuse cycles with minimal activity loss. The bibliographic analysis was conducted using the American Chemical Society (ACS) Scifinder^® database, the Elsevier B.V. Scopus^® database, and the Clarivate Analytics Web of Science^® database, under the institutional license of the Universidad Veracruzana. Keywords were searched for each section, generally limiting the document type to “reviews” and “journals,” and the language to English, and published between 2000 and 2025. Full article

The development of organic–inorganic hybrid materials bearing both acidic and basic functionalities is a challenging task, as it requires preserving the integrity and availability of two distinct active sites within a single porous network, such as silica. In this study, we report a synthetic approach that combines established grafting and co-condensation methods to achieve a controlled distribution of acidic and basic sites in mesoporous silica. Although each strategy is well known individually, their deliberate integration provides a distinctive pathway to tune the spatial arrangement and mutual preservation of the two functionalities. A comprehensive, multi-technique characterization approach, including in situ analyses and probe molecule adsorption, was used to monitor structural and chemical changes in both the organic and inorganic components. The results reveal that the coexistence of acidic and basic groups is highly sensitive to the synthetic conditions and activation treatments. In particular, basic sites are prone to protonation during the conversion of thiol groups into strong sulphonic acid sites, resulting in a partial loss of basic activity. The extent of this effect depends on the specific preparation route. In conclusion, the combined synthetic and characterization approach offers valuable insights into the nature, stability, and availability of the functional sites, guiding the rational design of advanced bifunctional hybrid materials. Full article

As key intermediate products in petroleum and chemical units, C4 hydrocarbons can be converted to ethene and propylene. While C4 olefins can be cracked into ethene and propylene on acid catalysts, such reactions with C4 paraffins are difficult under these conditions. In this study, a bifunctional metal–acid catalyst, BDHC, was prepared for catalytic dehydrogenation and catalytic cracking, using ZSM-5 zeolite for cracking active groups and Fe₂O₃ and Cr₂O₃ for dehydrogenation active groups. In the catalyzed reaction, C4 paraffins are converted to C4 olefins, which are subsequently cracked into ethene and propylene. The BDHC catalyst’s high relative crystallinity and large specific surface area and pore volume promote adsorption of reactant molecules. Moreover, the appropriate acid content suppresses side pathways and produces more ethene and propylene. Under optimized conditions, the ethene yield was 11.20%, the propylene yield was 27.51%, and the sum of the ethene and propylene yields was 38.71%. Full article

Engineering of a bifunctional enzyme that combines DNA-dependent DNA polymerase and reverse transcriptase (RT) activities is a highly promising biotechnological goal, as it would enable one-enzyme RT-PCR. For this purpose, we selected the high-fidelity Pyrococcus furiosus (Pfu) DNA polymerase as engineering scaffold. The selection of amino acid residues for replacement was carried out based on a multi-sequence alignment of diverse DNA polymerases and literature data, which allowed us to target amino acids, which presumably are triggers of the RT activity appearance. Six mutant variants of the Pfu enzyme were created and their activity was analyzed. Through enzymatic screening, we identified the Pfu-M6 variant, which exhibits dual DNA-dependent and RNA-dependent DNA polymerase activity. This thermostable enzyme retains its inherent DNA polymerase function and has acquired the ability to catalyze reverse transcription under standard PCR conditions, which allows the created mutant form to be used for efficient amplification of DNA starting from an RNA template. Full article

Non-precious catalysts for alkaline hydrogen evolution reaction (HER) face a fundamental multi-scale challenge: lack of synergy between electronic structure tuning for balancing H adsorption and water dissociation, active site stabilization for boosting intrinsic turnover frequency (TOF), and mass transport. Even Pt loses 2–3 orders of magnitude activity in alkaline media due to inefficient water dissociation, a synergistic gap unresolved by the Sabatier principle alone. Existing strategies only address isolated aspects: phase engineering optimizes electronic structure but not active site stability; heteroatom doping introduces defects unlinked to mass transport; and nanostructuring enhances mass transfer but not atomic-level activity. None of them address multi-scale mechanistic synergy. Herein, we design a hierarchically porous P-doped NiCo alloy (hpP-NiCo) with an aim of achieving this synergy via integrating α-FCC/ε-HCP phases, P-induced defects, and 3D porosity. The formed α/ε interface tunes the d-band center to balance H adsorption and water dissociation; and the doped P stabilizes metal-vacancy sites to boost TOF. In addition, porosity matches mass transport with active site accessibility. In 1 M KOH, hpP-NiCo reaches 1000 mA cm⁻² at 185 mV overpotential and has a Tafel slope of 43.1 mV dec⁻¹, corresponding to electrochemical desorption as the rate-limiting step and verifying Volmer acceleration. Moreover, it also exhibits bifunctional oxygen evolution reaction (OER), achieving 100 mA cm⁻² at potential of 1.55 V. This work establishes a mechanistic synergy model for non-precious HER catalysts. Full article

This study introduces nitrogen- and silicon-containing carbon quantum dots (N,Si-CQDs), synthesized hydrothermally from the sustainable bioresource stinging nettle (Urtica dioica L.), as chemically active supports for Pt, Pd, and Pt₃Pd₁ electrocatalysts. The N,Si-CQDs were characterized by a high concentration of N/O surface functionalities and the presence of biogenic Si. A significant finding is that, with this support, biogenic Si acts as a nucleation template: Pd forms in situ as orthorhombic Pd₉Si₂ nanorods alongside spherical particles, whereas Pt predominantly develops as cubic/quasi-cubic crystals. This templating process promotes faceted (cubic) Pt₃Pd₁ alloy nanoparticles with robust interfacial contact with the support and a log-normal size distribution (14.2 ± 4.3 nm) on N,Si-CQDs (4.7 ± 1.4 nm). This configuration enhanced the electrochemically active surface area to 181 m² gPt⁻¹, significantly exceeding those of commercial Pt₁Pd₁/XC-72 (27.7 m² gPt⁻¹) and monometallic Pt/N,Si-CQDs (14.3 m² gPt⁻¹). Consequently, the catalyst demonstrated superior methanol oxidation performance, evidenced by a low onset potential (0.17 V), approximately 10-fold higher mass activity compared to Pt₁Pd₁/XC-72, and 53% activity retention after a 16 h accelerated durability test. The enhanced performance is attributed to the strong nanoparticle anchoring by N,Si-CQDs, the bifunctional/ligand effects of the Pt–Pd alloy that improve CO tolerance, and the templating role of biogenic Si. Full article

The rational design of multifunctional electrocatalysts requires synergistic integration of conductive scaffolds with redox-active components. Here, a hierarchical core–shell NiCo₂S₄ grown/anchored on Co₉S₈-loaded carbon nanofibers (NCS/CS/CNFs) was synthesized via an electrospinning and hydrothermal approach and systematically characterized. FESEM/TEM confirmed a core-shell nanofiber structure with a NiCo₂S₄ shell thickness of ~30–70 nm, increasing the fiber diameter to ~290 ± 30 nm, while BET analysis revealed a surface area of 24.84 m² g⁻¹ and pore volume of 0.042 cm³ g⁻¹, surpassing CS/CNFs (6.12 m² g⁻¹) and NCS (4.85 m² g⁻¹). XRD confirmed crystalline NiCo₂S₄ and Co₉S₈ phases, while XPS identified mixed Ni²⁺/Ni³⁺ and Co²⁺/Co³⁺ states with strong Ni-S/Co-S bonding, indicating enhanced electron delocalization. Electrochemical measurements in 1 M KOH demonstrated outstanding OER activity, with NCS/CS/CNFs requiring only 324 mV overpotential at 10 mA cm⁻², a Tafel slope of 125.7 mV dec⁻¹, and low charge-transfer resistance (0.33 Ω cm²). They also achieved a high areal capacitance of 1412.5 μF cm⁻² and maintained a stable current density for >5 h. For methanol oxidation, the composite delivered 150 mA cm⁻² at 0.1 M methanol, ~1.6 times that of CS and 1.3 times that of NCS, while maintaining stability for 18,000 s. This bifunctional activity underscores the synergy between conductive CNFs and hierarchical sulfides, offering a scalable route to durable electrocatalysts for water splitting and direct methanol fuel cells. Full article

Developing bifunctional electrocatalysts that simultaneously enable green hydrogen production and water purification is essential for advancing sustainable energy and environmental technologies. In this study, we present Cu@Pd core–shell nanostructures fabricated through template-assisted electrodeposition of Cu, followed by galvanic Pd modification on pyrolytic graphite electrodes (PGEs). The optimised catalyst exhibited superior hydrogen evolution reaction (HER) activity, with an onset potential of 70 mV, a low Tafel slope of 33 mV dec⁻¹ and excellent stability during prolonged HER operation. In addition to hydrogen evolution, Cu@Pd/PGE shows significantly enhanced nitrate reduction reaction (NRR) activity compared to Cu/PGE in both alkaline and neutral conditions. Under ideal conditions, the catalyst achieved 60% nitrate removal with high selectivity towards ammonia and minimal nitrite formation, emphasising its superior performance. This enhanced bifunctionality arises from the synergistic Cu–Pd interface, facilitating efficient nitrate adsorption and selective hydrogenation. Despite their high catalytic activity for both HER and NRR, the Cu@Pd nanostructures could often emerge as a versatile platform for integration into sustainable hydrogen production and an effective denitrification process. Full article

Electrochemical water splitting has emerged as a pivotal strategy for advancing sustainable and renewable energy technologies. However, its practical deployment is often hampered by sluggish reaction kinetics, large overpotentials, and the high cost of efficient electrocatalysts. To overcome these critical challenges, a novel bifunctional electrocatalyst based on electropolymerized CeO₂-NiO with polyacrylic acid (Ce-Ni-PAA) has been rationally engineered for overall water splitting. The strategic incorporation of conductive polymer framework enables effective modulation of the local electronic structure, enhances charge transport pathways, and maximizes the density of electrochemically accessible active sites, thereby substantially boosting catalytic performance. When evaluated in a 1 M KOH alkaline medium, the optimized Ce-Ni-PAA_0.5/NF hybrid demonstrates remarkable catalytic activity with 366.5 mV overpotential at 50 mA cm⁻², coupled with lower Tafel slope of 93.5 mV dec⁻¹. Additionally, the Ce-Ni-PAA_0.5/NF electrocatalyst exhibits exceptional ECSA of 1092.3 cm², which confirms the presence of a significantly larger number of electrochemically active sites. The electrocatalyst retains its performance even after 5000 continuous cycles of operation. The superior performance is attributed to the synergistic effects arising from the enriched composition, efficient electron transport channels, and abundant catalytic centers. Collectively, this study not only highlights the significance of rational structural and compositional design but also offers valuable insights toward the development of next-generation, cost-effective bifunctional electrocatalysts with strong potential for scalable water splitting and clean energy applications. Full article