Photoswitching-Modulated Interfacial Electron Transfer in Single-Atom Co-TiO for Enhanced Pollutant Mineralization in Persulfate-Based AOPs.

Precise modulation of interfacial electron transfer in heterogeneous catalysts is crucial for efficient degradation of persistent organic pollutants in persulfate-based advanced oxidation processes. In this work, we introduced a photoswitching strategy that in situ regulates electron transfer in single-atom Co-TiO catalysts, optimizing the production of reactive oxidative species during peroxymonosulfate (PMS) activation, thereby improving pollutant mineralization efficiency. Theoretical calculations revealed that the formation of high-valent Co-oxo species during PMS activation was thermodynamically favorable.

Engineering Spin State of Atomic Iron Centers for High-Performance Photocatalytic Nitrogen Fixation.

Electronic structures fundamentally influence material properties, with electron spin playing a pivotal role in defining catalytic activity and reaction pathways. However, the precise spin-mediated mechanisms of adsorption energies and nitrogen-nitrogen transition states on the catalyst surface, remain unclear due to the complexity of spin-mediated promotion factors. Herein, we demonstrate that tuning the spin state of single iron (Fe) sites on TiO can significantly enhance photocatalytic nitrogen reduction reaction (NRR).

Tailoring Interfacial Active Sites and Valence States via Ligand Modulation in ZIF-Derived Catalysts for Enhanced Fenton-like Reactions.

Zeolitic imidazolate framework (ZIF)-derived catalysts have emerged as promising materials for Fenton-like advanced oxidation processes aimed at the degradation of persistent organic pollutants. However, the impact of the ligand chemistry on the interfacial properties and catalytic performance of these materials remains underexplored. Herein, Fe-doped ZIF precursors (ZIF-7/8/90) with different imidazolate ligands were pyrolyzed to obtain corresponding carbon-supported catalysts (ZIF-7/8/90-Fe-900) and evaluated under environmentally relevant water treatment conditions.

Selective Conversion of Lignin Wastes into High-Value Aromatics: Catalyst Design and Process Sustainability Evaluation.

Lignin, the most abundant natural source of aromatic scaffolds, is a main byproduct or waste of the pulping industry with an annual output of 50 million tons. In this work, an efficient reductive depolymerization approach is proposed for the selective conversion of lignin waste into guaiacols. We rationally design an efficient Ru-based catalyst by creating a chemically active surface of the nitrogen-doped carbon (NC) support via dispersing single Zn metal atoms on it and then supporting the Ru nanoparticles with enhanced electronic metal-support interactions (EMSIs).

Recyclable Quasi-Homogeneous Carbon Nitride Colloidal Catalyst for Sustainable Photocatalytic HO Generation.

Graphitic carbon nitride (g-CN) photocatalysts have attracted growing interest for the eco-friendly, solar-driven synthesis of hydrogen peroxide (HO). However, the catalytic efficiency remains limited by poor accessibility of reactive sites due to the hydrophobic nature and aggregation tendency of conventional g-CN. Here, we report a hydrophilic g-CN colloidal photocatalyst, synthesized via potassium ion (K⁺) incorporation and surface grafting with sulfonylcyanide groups, which enables quasi-homogeneous photocatalytic HO production (7,886 µmol g⁻¹ h⁻¹), surpassing most reported g-CN-based heterogeneous systems.

Anions-Impacted Water Purification from a Dual-Substrate Perspective.

Heterogeneous chemical oxidation for water treatment based on direct electron transfer has attracted great interest due to its low oxidant consumption and selective oxidation capabilities. Under low oxidant dosages (e.g.

Quantifying assembly processes of dissolved organic matter pools in eutrophication using high-resolution mass spectrometry and ecological models.

Dissolved organic matter (DOM) represents a large, dynamic pool of carbon, playing a crucial role in eutrophic aquatic ecosystems through its continuous transport and transformation. However, the assembly mechanisms of DOM under different eutrophic conditions remain elusive, hindering the understanding of carbon dynamics and the prediction of carbon fate. Here we collected 72 lake water samples during two sampling events in Chaohu Lake, the fifth largest freshwater lake in China, and performed high-resolution mass spectrometry (HRMS) and ecological null modeling to quantify the assembly processes of DOM in eutrophication.

Homonuclear/Heteronuclear Bimetallic Conjugated Coordination Polymers with Customized Oxygen Evolution Pathway.

The reasons for the generally superior performance of synergistic effects in bimetallic catalysts in the oxygen evolution reaction (OER) are not fully understood, largely due to the complexity of catalyst structures and the challenges associated with synthesizing long-range atomic ordering catalysts. In this study, we present a series of two-dimensional (2D) conjugated bimetallic coordination polymers (c-CPs) involving Co or Ni with unambiguous and nearly identical geometry structures for the electrocatalysis of OER, which are highly suitable for discussions on structure-property correlations. The heteronuclear unexpectedly alters the OER catalytic mechanisms from adsorbate evolution mechanism those observed in homonuclear and to the kinetically faster oxide path mechanism, exhibiting high stability and an ultralow overpotential of 282 mV even at 100 mA cm with a Tafel slope of approximately 42 mV dec.

Molecular Descriptor for Catalytic Direct Oxidative Transfer Process Based on Thermodynamic State Changes during Reactions.

The direct oxidative transfer process (DOTP) in heterogeneous catalytic persulfate oxidation (HCPO) systems has gained increasing attention. In this process, the reaction rate is linked to pollutant properties, and identifying this correlation through descriptors offers insights into reaction mechanisms and water treatment strategies. However, most of the existing descriptors are based on static molecular properties and show limited correlation with reactivity and mechanisms.

Optimization of ultrasound-assisted deep eutectic solvents extraction of rutin from Ilex asprella using response surface methodology.

Taking the extraction amount of rutin as the index, the extraction process of rutin from Ilex asprella (Hook. et Arn.) Champ.

Electrocatalytic Hydrogenation Boosted by Surface Hydroxyls-Modulated Hydrogen Migration over Nonreducible Oxides.

The migration of atomic hydrogen species over heterogeneous catalysts is deemed essential for hydrogenation reactions, a process closely related to the catalyst's functionalities. While surface hydroxyls-assisted hydrogen spillover is well documented on reducible oxide supports, its effect on widely-used nonreducible supports, especially in electrocatalytic reactions with water as the hydrogen source, remains a subject of debate. Herein, a nonreducible oxide-anchored copper single-atom catalyst (Cu/SiO) is designed and uncover that the surface hydroxyls on SiO can serve as efficient transport channels for hydrogen spillover, thereby enhancing the activated hydrogen coverage on the catalyst and favoring the hydrogenation reaction.

Tunable control of Cas12 activity promotes universal and fast one-pot nucleic acid detection.

The CRISPR-based detection methods have been widely applied, yet they remain limited by the non-universal nature of one-pot diagnostic approaches. Here, we report a universal one-pot fluorescent method for the detection of epidemic pathogens, delivering results within 15-20 min. This method uses heparin sodium to precisely tunes the cis-cleavage capability of Cas12 via interference with the Cas12a-crRNA binding process, thereby generating significant fluorescence due to the accumulation of isothermal amplification products.

Electrocatalytic Biomass Oxidation via Acid-Induced In Situ Surface Reconstruction of Multivalent State Coexistence in Metal Foams.

Electrocatalytic biomass conversion offers a sustainable route for producing organic chemicals, with electrode design being critical to determining reaction rate and selectivity. Herein, a prediction-synthesis-validation approach is developed to obtain electrodes for precise biomass conversion, where the coexistence of multiple metal valence states leads to excellent electrocatalytic performance due to the activated redox cycle. This promising integrated foam electrode is developed via acid-induced surface reconstruction to in situ generate highly active metal (oxy)hydroxide or oxide (MOH or MO) species on inert foam electrodes, facilitating the electrooxidation of 5-hydroxymethylfurfural (5-HMF) to 2,5-furandicarboxylic acid (FDCA).

Deciphering unique enzymatic pathways in sulfonamide biotransformation by direct ammonia oxidizer Alcaligenes ammonioxydans HO-1.

Heterotrophic nitrification, similar to autotrophic nitrification, involves key enzymes and reactive nitrogen intermediates during ammonia oxidation, which may influence antibiotic transformation. However, the interference between antibiotic transformation products from ammonia oxidation and secondary metabolites in heterotrophic nitrifiers makes antibiotic transformation pathways more complicated. In this work, we observe that the heterotrophic nitrifier Alcaligenes ammonioxydans HO-1 can effectively convert sulfonamide antibiotics.

Directional Electron Transfer in Enzymatic Nano-Bio Hybrids for Selective Photobiocatalytic Conversion of Nitrate.

Semi-artificial photosynthetic system (SAPS) that combines enzymes or cellular organisms with light-absorbing semiconductors, has emerged as an attractive approach for nitrogen conversion, yet faces the challenge of reaction pathway regulation. Herein, we find that photoelectrons can transfer from the -C≡N groups at the edge of cyano-rich carbon nitride (g-CN-CN) to nitrate reductase (NarGH), while the direct electron transfer to nitrite reductase (cdNiR) is inhibited due to the physiological distance limit of active sites (>14 Å). By means of the directional electron transfer between g-CN-CN and extracted biological enzymes, the product of the denitrification reaction was switched from inert N to usable nitrite with an unprecedented selectivity of up to 95.

In Situ Quantitative Monitoring of Adsorption from Aqueous Phase by UV-vis Spectroscopy: Implication for Understanding of Heterogeneous Processes.

The development of in situ techniques to quantitatively characterize the heterogeneous reactions is essential for understanding physicochemical processes in aqueous phase. In this work, a new approach coupling in situ UV-vis spectroscopy with a two-step algorithm strategy is developed to quantitatively monitor heterogeneous reactions in a compact closed-loop incorporation. The algorithm involves the inverse adding-doubling method for light scattering correction and the multivariate curve resolution-alternating least squares (MCR-ALS) method for spectral deconvolution.

Nanoconfinement steers nonradical pathway transition in single atom fenton-like catalysis for improving oxidant utilization.

The introduction of single-atom catalysts (SACs) into Fenton-like oxidation promises ultrafast water pollutant elimination, but the limited access to pollutants and oxidant by surface catalytic sites and the intensive oxidant consumption still severely restrict the decontamination performance. While nanoconfinement of SACs allows drastically enhanced decontamination reaction kinetics, the detailed regulatory mechanisms remain elusive. Here, we unveil that, apart from local enrichment of reactants, the catalytic pathway shift is also an important cause for the reactivity enhancement of nanoconfined SACs.

Circumventing bottlenecks in HO photosynthesis over carbon nitride with iodine redox chemistry and electric field effects.

Artificial photosynthesis using carbon nitride (g-CN) holds a great promise for sustainable and cost-effective HO production, but the high carrier recombination rate impedes its efficiency. To tackle this challenge, we propose an innovative method involving multispecies iodine mediators (I/I) intercalation through a pre-photo-oxidation process using potassium iodide (suspected deteriorated "KI") within the g-CN framework. Moreover, we introduce an external electric field by incorporating cationic methyl viologen ions to establish an auxiliary electron transfer channel.

Tailoring d-band center of high-valent metal-oxo species for pollutant removal via complete polymerization.

Polymerization-driven removal of pollutants in advanced oxidation processes (AOPs) offers a sustainable way for the simultaneous achievement of contamination abatement and resource recovery, supporting a low-carbon water purification approach. However, regulating such a process remains a great challenge due to the insufficient microscopic understanding of electronic structure-dependent reaction mechanisms. Herein, this work probes the origin of catalytic pollutant polymerization using a series of transition metal (Cu, Ni, Co, and Fe) single-atom catalysts and identifies the d-band center of active site as the key driver for polymerization transfer of pollutants.

Reduced Lattice Constant in Al-Doped LiMnO Nanoparticles for Boosted Electrochemical Lithium Extraction.

Extracting lithium selectively and efficiently from brine sources is crucial for addressing energy and environmental challenges. The electrochemical system employing LiMnO (LMO) electrodes has been recognized as an effective method for lithium recovery. However, the lithium selectivity and stability of LMO need further enhancement for its practical applications.

Constructing sulfur and oxygen super-coordinated main-group electrocatalysts for selective and cumulative HO production.

Direct electrosynthesis of hydrogen peroxide (HO) via the two-electron oxygen reduction reaction presents a burgeoning alternative to the conventional energy-intensive anthraquinone process for on-site applications. Nevertheless, its adoption is currently hindered by inferior HO selectivity and diminished HO yield induced by consecutive HO reduction or Fenton reactions. Herein, guided by theoretical calculations, we endeavor to overcome this challenge by activating a main-group Pb single-atom catalyst via a local micro-environment engineering strategy employing a sulfur and oxygen super-coordinated structure.

Interfacial Electron Transfer in Chemical and Biological Transformation of Pollutants in Environmental Catalysis.

Interfacial electron transfer (IET) is essential for chemical and biological transformation of pollutants, operative across diverse lengths and time scales. This Perspective presents an array of multiscale molecular simulation methodologies, supplemented by in situ monitoring and imaging techniques, serving as robust tools to decode IET enhancement mechanisms such as interface molecular modification, catalyst coordination mode, and atomic composition regulation. In addition, three IET-based pollutant transformation systems, an electrocatalytic oxidation system, a bioelectrochemical spatial coupling system, and an enzyme-inspired electrocatalytic system, were developed, demonstrating a high effect in transforming and degrading pollutants.

Unraveling heterogeneity of dissolved organic matter in highly connected natural water bodies at molecular level.

The exploring of molecular-level heterogeneity of dissolved organic matter (DOM) in highly connected water bodies is of great importance for pollution tracing and lake management, and provides new perspectives on the transformations and fate of DOM in aquatic systems. However, the inherent homogeneity of DOM in connected water bodies poses challenges for its heterogeneity analysis. In this work, an innovative method combining fluorescence spectroscopy, high-resolution mass spectrometry (HRMS), and cluster analysis was developed to reveal the heterogeneity of DOM in highly connected water bodies at the molecular level.