Boosting Photocatalytic Upcycling of Liquid Biomass into Biodiesel via Microenvironment Modulation

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 13, 2024

Abstract The rational design of a photocatalyst and its microenvironmental modulation is crucial in the heterogeneous photocatalysis process, yet relevant research on photocatalytic biodiesel synthesis not explored. Herein, based prediction density functional theory (DFT) calculations, highly efficient ternary biocompatible montmorillonite (Mt) nanocomposites S‐scheme heterojunction photocatalysts (g‐C 3 N 4 ‐TiO 2 @Mt, CTM) are successfully rationally designed. By modulating microenvironment production, CTM‐2 demonstrates exceptional catalytic performance stability, achieving record‐breaking yield 98.5%. Through ex/in situ X‐ray photoelectron spectroscopy (XPS), absorption near‐edge (XANES), theoretical formation revealed, which can generate an interface electric field (IEF) that provides intrinsic driving force for carrier migration enhances surface positivity. This boosts enrichment effect electronegative oleic acid (OA) carboxyl molecules, thus greatly enriching substrate concentration improving reaction microenvironment. Moreover, fourier transform infrared spectrometer (FT‐IR)/Raman together with electron paramagnetic resonance (EPR) further confirm key intermediates CH O• ester carbonyl (C═O), DFT calculations provide reference pathway, determined to be capable significantly reducing energy barrier rate‐determining step.

Language: Английский

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Water Spillover to Expedite Two‐Electron Oxygen Reduction

Advanced Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 5, 2025

Abstract Limited by the activity‐selectivity trade‐off relationship, electrochemical activation of small molecules (like O 2 , N 2, and CO ) rapidly diminishes Faradaic efficiencies with elevated current densities (particularly at ampere levels). Nevertheless, some catalysts can circumvent this restriction in a two‐electron oxygen reduction reaction (2e − ORR), sustainable pathway for activating to hydrogen peroxide (H ). Here we report 2e ORR expedited fluorine‐bridged copper metal–organic framework catalyst, arising from water spillover effect. Through operando spectroscopies, kinetic theoretical characterizations, it demonstrates that under neutral conditions, plays dual role accelerating dissociation stabilizing key * OOH intermediate. Benefiting spillover, catalyst expedite density range 0.1–2.0 A cm −2 both high (99–84.9%) H yield rates (63.17–1082.26 mg h −1 Further, feasibility present system has been demonstrated scaling up unit module cell 25 combination techno‐economics simulations showing production cost strongly dependent on densities, giving lowest price $0.50 kg 2.0 . This work is expected provide an additional dimension leverage systems independent oftraditional rules.

Language: Английский

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Enhancing Electrocatalytic Activity Through Targeted Local Electrolyte Micro‐Environment

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 10, 2025

Abstract The local electrolyte micro‐environment surrounding the catalyst reaction center, including critical factors such as pH, reactant concentration, and electric field, plays a decisive role in electrocatalytic reactions water splitting. Recently, this topic has garnered significant attention due to its potential significantly enhance catalytic performance. While various strategies optimize processes have been explored, deliberate control over fundamental principles guiding these adjustments remain their early stages of development. This review provides comprehensive examination key efforts aimed at designing tailoring localized micro‐environments improve It discusses advances micro‐environmental design, methodologies for evaluating shifts, mechanistic insights driving developments. Additionally, highlights existing challenges prospective industrial applications strategies. By offering detailed analysis recent developments, aims equip researchers with practical knowledge on controlling micro‐environments, thereby accelerating progress toward real‐world processes.

Language: Английский

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Recent Progress in Oxygen Reduction Reaction Toward Hydrogen Peroxide Electrosynthesis and Cooperative Coupling of Anodic Reactions

Advanced Materials, Journal Year: 2025, Volume and Issue: unknown

Published: March 13, 2025

Abstract Electrosynthesis of hydrogen peroxide (H 2 O ) via two‐electron oxygen reduction reaction (2e − ORR) is a promising alternative to the anthraquinone oxidation process. To improve overall energy efficiency and economic viability this catalytic process, one pathway develop advanced catalysts decrease overpotential at cathode, other couple 2e ORR with certain anodic reactions full cell voltage while producing valuable chemicals on both electrodes. The performance catalyst depends not only material itself but also environmental factors. Developing electrocatalysts high selectivity activity prerequisite for efficient H electrosynthesis, coupling appropriate would further enhance efficiency. Considering this, here comprehensive review presented latest progress state‐of‐the‐art in different media, microenvironmental modulation mechanisms beyond design, as well electrocatalytic system various reactions. This presents new insights regarding existing challenges opportunities within rapidly advancing field, along viewpoints future development electrosynthesis construction green roadmaps.

Language: Английский

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Orbital electron delocalization of axial-coordinated modified FeN₄ and structurally ordered PtFe intermetallic synergistically for efficient oxygen reduction reaction catalysis

Chemical Science, Journal Year: 2024, Volume and Issue: 15(32), P. 12989 - 13000

Published: Jan. 1, 2024

A harmonious axial-coordinated Pt x Fe/FeN 4 CCl catalyst was designed and fabricated by a simple method, integrating structurally ordered PtFe intermetallic with an orbital electron-delocalization FeN4CCl support for synergistic ORR catalysis.

Language: Английский

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Observation of O₂ Molecules Inserting into Fe–H Bonds in a Ferrous Metal–Organic Framework

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 21, 2025

Exploring the interactions between oxygen molecules and metal sites has been a significant topic. Most previous studies concentrated on enzyme-mimicking interacting with O2 to form M-OO species, leaving development of new types O2-activating novel adsorption mechanisms largely overlooked. In this study, we reported an Fe(II)-doped metal-organic framework (MOF) [Fe3Zn2H4(bibtz)3] (MAF-203, H2bibtz = 1H,1'H-5,5'-bibenzo[d][1,2,3]triazole), featuring unprecedented tetrahedral Fe(II)HN3 site. This MOF exhibits selective behavior for from air, achieving O2/N2 separation selectivity up 67.1. Breakthrough experiments confirmed that MAF-203 can effectively capture air even under high relative humidity 60%. X-ray absorption spectroscopy, in situ diffuse reflectance infrared Fourier transform spectra, ab initio molecular dynamics simulations were utilized monitor loading process Interestingly, could insert into Fe-H bonds FeIIHN3 sites, forming FeIII-OOH species (instead commonly observed Fe-OO species) ultrahigh enthalpy -99.2 kJ mol-1. Consequently, enables efficient electrochemical 2e- reduction production H2O2 as feedstock. Specifically, solid-state electrolyte electrolyzer without any liquid electrolyte, achieved continuous medical-grade (3.2 wt %) solution salts 70 h, performance comparable pure conditions. The activation inaugurate fresh chapter grasping interaction sites.

Language: Английский

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Bypassing gas-liquid mass transfer resistance in a Fenton wet scrubber for boosting the removal of hydrophobic styrene: Construction of a novel gas-solid-liquid triple-phase interface

Chemical Engineering Journal, Journal Year: 2025, Volume and Issue: unknown, P. 160166 - 160166

Published: Feb. 1, 2025

Language: Английский

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Zinc hydroxide–organic framework for electrochemical synthesis of H2O2

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Zinc hydroxide-organic framework nanosheets were synthesized as a 2e-ORR electrocatalyst, delivering high H 2 O productivity and Faraday efficiency in an alkaline electrolyte.

Language: Английский

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Efficient H₂O₂ Electrosynthesis in Acidic media via Multiscale Catalyst Optimization

Advanced Materials, Journal Year: 2025, Volume and Issue: unknown

Published: March 18, 2025

Abstract Electrochemically generating hydrogen peroxide (H 2 O ) from oxygen offers a more sustainable and cost‐effective alternative to conventional anthraquinone process. In alkaline conditions, H is unstable as HO − , in neutral electrolytes, alkali cation crossover causes system instability. Producing acidic electrolytes ensures enhanced stability efficiency. However, the reduction reaction mechanism dominated by inner‐sphere electron transfer pathway, requiring careful consideration of both mass kinetics. These stringent requirements limit production efficiency, typically below 10–20% at industrial‐relevant current densities (>300 mA cm −2 ). Using multiscale approach that combines active site tuning with macrostructure tuning, this work presents an octahedron‐like cobalt structure on interconnected hierarchical porous nanofibers, achieving faradaic efficiency exceeding 80% 400 stable operation for over 120 h 100 . At 300 optimized catalyst demonstrates cell potential 2.14 V, resulting energy 26%.

Language: Английский

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Rapidly Constructing Meter‐Scale Single‐Molecule Integrated Catalytic Electrode with Hydrophobic Microenvironment for pH‐Universal CO₂ Electroreduction

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: March 21, 2025

Abstract The massive production of cost‐effective and highly‐efficient electrode materials is crucial for industrial CO 2 electroconversion. Herein, this work breaks away from conventional approaches by directly constructing an integrated single‐molecule catalytic (7F‐CoPc@GF) at the meter scale, through integration π‐extended macrocyclic structures into commercial carbon‐based collectors with strong interfacial interactions. This innovative method reshapes traditional design using a liquid‐phase self‐adaptive anchoring strategy, eliminating need conductive adducts binders. In addition, introducing perfluoroalkyl chain, built‐in hydrophobic microenvironment in heterogenized macrocycles optimizes electron migration water interaction around active sites, suppressing hydrogen evolution reaction thereby enhancing pH‐universal electroreduction across broad potential range. Significantly, mechanistic study reveals that not only enhances effective collisions between sites reactants but also facilitates immediate removal products surface. Further development dual value‐added electrolysis systems, incorporating waste gas treatment, highlights versatility extensibility meter‐scale material. These findings offer promising methodology rational stable, binder‐free, large‐size electrodes, advancing sustainable scale.

Language: Английский

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