Reactive Hydroxyl Research Articles

Photodegradation of RB5 dye with modified zeolites: influence of temperature and UV irradiation

Abstract This study explores the photocatalytic degradation of Reactive Black 5 (RB5) dye using thermally modified natural zeolites, aiming to improve water purification methods. Zeolites were calcined at 250 °C, 350 °C, and 500 °C, and characterized through x–ray diffraction (XRD), Scanning Electron Microscopy (SEM), and Fourier Transform Infrared Spectroscopy (FTIR) to analyze their structural and morphological transformations. The results reveal that calcination significantly enhances the photocatalytic performance, particularly for ZNM500, which exhibited the highest efficiency, reaching a 60% removal rate of RB5. The degradation process follows a pseudo-first-order kinetic model at lower dye concentrations but adheres more closely to the Langmuir–Hinshelwood equation at higher concentrations, emphasizing the role of surface adsorption in catalysis. UV irradiation was a key factor in boosting reaction rates, with shorter wavelengths (254 nm) providing greater energy, leading to more effective dye breakdown by facilitating the generation of reactive hydroxyl radicals (·OH). These findings suggest that thermally modified zeolites, especially ZNM500, represent a promising solution for wastewater treatment, offering an efficient, cost–effective, and environmentally friendly approach to removing synthetic dyes from contaminated water sources.

Expansion of d-spacing of boehmite for enhanced phosphate adsorption via hydrogen bond network

The optimization of the interlayer water content to increase the d-spacing of layered materials has recently attracted interest in pollutant removal. Several studies have explored phosphate adsorption onto boehmite considering its high surface area; however, the influence of its d-spacing on the adsorption performance remains unexplored. Therefore, our study aimed to investigate the impact of the synthesis pH of boehmite on the d-spacing and adsorption performance of phosphate ions. For this purpose, boehmite samples were synthesized under various pH conditions at 100°C to be tested for phosphate adsorption. As a result of this mild synthesis condition, the number of reactive hydroxyl groups in boehmite samples ranged from 7.02 – 9.02mmol/g, nearly four times higher than the reported boehmites. Boehmite prepared under acidic conditions exhibits a relatively high interlayer water content and an enlarged d-spacing from 0.640 to 0.996nm, resulting in superior phosphate adsorption (215mg/g) within one minute. We also confirmed that phosphate adsorption increased the binding energy states of aluminum and oxygen in boehmite, indicating a robust hydrogen bond network with phosphate ions in the inner space. In contrast, the adsorption decreased the binding energy for other types of boehmite, indicating charge interaction. Competitive adsorption tests also showed the strong affinity of boehmite for phosphate ions, even in the presence of fluoride ions. These findings highlight the importance of the interlayer water molecules in controlling the d-spacing of boehmite, indicating their critical role in removing anions from water.

Dipropyl sulfide optimized buried interface to improve the performance of inverted perovskite solar cells

Recently, [4–(3,6-dimethyl-9H-carbazol-9-yl)butyl] phosphonic acid (Me-4PACz) has garnered significant attention as a highly effective passivation layer for NiOx. However, the Me-4PACz passivation layer shows low wettability to perovskite precursors, hindering the crystallization of perovskite. Moreover, Me-4PACz does not uniformly and completely cover NiOx, failing to achieve an optimal passivation effect. The presence of high-valence-state Ni species and reactive hydroxyls on the NiOx film surface leads to perovskite degradation. To address this, dipropyl sulfide (DPS) was incorporated into a solution of Me-4PACz. This approach not only enhances the wettability of Me-4PACz, facilitating the growth of larger perovskite grains but also enables Me-4PACz to form a homogeneous passivation layer with strong coverage. This effectively prevents direct contact between NiOx and perovskite films. Additionally, DPS interacts with reactive hydroxyls, removing them from the NiOx surface and mitigating the deprotonation reaction of MA/FA in perovskite. Furthermore, DPS is reducible, which helps in reducing high-valent Ni (Ni4+), thereby decreasing redox reactions at the interface. As a result, the optimized perovskite solar cells with DPS achieved a power conversion efficiency (PCE) of 22.29%, higher than the control device of 20.52%. Moreover, the DPS-decorated device demonstrated excellent stability, retaining over 80% of its initial PCE value, compared to only 60% retention in the control device. This work modified the buried interface and offers valuable insights for subsequent similar studies.

A tailored cytochrome P450 monooxygenase from Gordonia rubripertincta CWB2 for selective aliphatic monooxygenation.

Cytochrome P450 monooxygenases are recognized as versatile biocatalysts due to their broad reaction capabilities. One important reaction is the hydroxylation of non-activated C-H bonds. The subfamily CYP153A is known for terminal hydroxylation reactions, giving access to functionalized aliphatics. Whilst fatty derivatives may be converted by numerous enzyme classes, midchain aliphatics are seldomly accepted, a prime property of CYP153As. We report here on a new CYP153A member from the genome ofthe mesophilic actinobacterium Gordonia rubripertincta CWB2 as an efficient biocatalyst. The gene was overexpressed inEscherichia coli and fused with a surrogate electron transport system from Acinetobacter sp. OC4. This chimeric self-sufficient whole-cell system could perform hydroxylation and epoxidation reactions: conversions of C6-C14 alkanes, alkenes, alcohols and of cyclic compounds were observed, yielding production rates of, e.g., 2.69 mM h-1 for 1-hexanol and 4.97 mM h-1 for 1,2-epoxyhexane. Optimizing the linker compositions between the protein units led to significantly altered activity. Balancing linker length and flexibility with glycine-rich and helix-forming linker units increased 1-hexanol production activity to 350 % compared to the initial linker setup with entirely helical linkers. The study shows that strategic coupling of efficient electron supply and a selective enzyme enables previously challenging monooxygenation reactions of midchain aliphatics.

Ozonation of the antiviral oseltamivir in wastewater effluent: Matrix effect, oxidation pathway, and toxicity assessment

The potential environmental impacts of commonly employed antiviral drugs and their byproducts have attracted attention but remain largely unexplored. In this study, ozone (O3) was used to remove the oseltamivir phosphate (OP), a widely used antiviral, from different water matrices, including secondary municipal wastewater effluent (WWE). Over 90 % of OP was removed from a buffer solution using 10 µM of O3 in a short reaction time (30 s), while pseudo-first-order kinetics constants (K) showed a strong linear relationship with the initial O3 dosage. The pH of the solution was found to be an important factor in the ozonation process since the degradation mechanisms and, thereby, the K values are affected by the structural conformations of OP (protonated or deprotonated forms), the generation of hydroxyl radicals (•OH) under mild basic conditions, and the depletion of O3 under extreme basic pH. In addition, common inorganic ions slightly affect the K values, but increasing the ionic strength negatively influences the degradation process. Organic components in WWE also reduced the efficiency; however, over 95 % of OP degradation was achieved using a ratio of O3 dosage to dissolved organic carbon (DOC) of 0.544 g O3 g–1 DOC. Finally, a degradation pathway was proposed based on the detection of byproducts formed by direct ozonation and hydroxylation reactions. Acute toxicity and genotoxicity assessments on ozonated matrices, especially the WWE sample, suggest that these byproducts have no potential toxic effects. All these findings strongly suggest that ozonation can effectively degrade antivirals in municipal effluents.

LuCl3/B(C6F5)3 Cocatalyzed Reductive Deoxygenation of Ketones, Aldehydes, Alcohols, and Ethers to Alkanes with Pinacolborane.

This report describes the LuCl3/B(C6F5)3 cocatalyzed reductive deoxygenation of 67 ketones, aldehydes, alcohols, and ethers to alkanes under mild conditions. The strategy tolerates reactive amino, hydroxyl, nitro, halogen, vinyl, and ester functional groups, and the results demonstrate rare chemoselective deoxygenation of α,β-unsaturated ketones. Isotopic labeling experiments, control experiments, and derivatization studies are used to elucidate the reaction mechanism.

Hydroxylation of Phenol by an Azomethine Quinoxaline Schiff Base Copper (II) Complex

Introduction: A binuclear azomethine quinoxaline Schiff base copper (II) complex, [Cu2LCl2], having square-planar environment around each copper (II), has been synthesized. Method: The coordination of the azomethine quinoxaline Schiff base with copper (II) and its structure was studied by various physicochemical and spectroscopic measurements. Results: Catalytic activity of this complex in phenol hydroxylation reaction has been examined using H2O2 as a green oxidant. Conclusion: Catalytic reaction conditions were optimized and under these conditions, 18.32 % conversion of phenol has been obtained for this catalyst

C–H bond activation over chitosan based Fe(III) and Ni(II) catalysts

Chitosan (Cs) supported heterogeneous catalysts of Fe(III) and Ni(II) is developed by the equimolar reaction of two schiff base ligands, L1 [Cs-HACP] and L2 [ANI-HACP] and Metal salts {where Metal = Fe(III) and Ni(II)}with chitosan. The L1 ligand is prepared by the reaction of chitosan (Cs) and ortho hydroxyl (HACP) acetophenone in methanol and L2 ligand is prepared by the condensation of aniline (ANI) and ortho hydroxyl acetophenone (HACP) in solvent free condition. The prepared catalysts {M-[Cs-L1-L2]Cl2} are characterized by different analytical techniques viz. scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), powder X-ray diffraction (XRD), Thermogravimetric analysis (TGA), Fourier transform infrared (FTIR), Raman, UV-VIS-NIR, X-ray photoelectron spectroscopy (XPS) and computational studies. The catalytic behavior of newly synthesized catalysts are tested for the C–H activation using 70 % tert-butyl hydroperoxide (TBHP). The best results are obtained for tetralin oxidation. The order of catalytic reactivity of {M-[Cs-L1-L2]Cl2}catalyst is in decreasing order: {Fe(III)-[Cs-L1-L2]Cl2} > {Ni(II)-[Cs-L1-L2]Cl2}. The {Fe(III)-[Cs-L1-L2]Cl2} gives maximum conversion 81.99 % of tetralin with 84.50 % selectivity of tetralone (T-lone) and 6.47 % selectivity of tetralol (T-lol) after 5 h of reaction at 80 °C temperature. The chitosan based heterogeneous catalyst is easy to separate and recover. It can be recycled seven times.

Molecular–level insights into the synergistic activation of peracetic acid by ultraviolet and ferrous ions for the degradation of sedimentation sludge water in drinking water treatment plants based on Fourier transform-ion cyclotron resonance mass spectrometry

Sedimentation sludge water (SSW) from sedimentation tanks in drinking water treatment plants contains significant amounts of dissolved organic matter (DOM) and precursors of disinfection byproducts, raising increasing concerns about the safety of finished water following SSW recycling. This study explores the alterations in bulk properties and molecular characteristics of DOM in SSW treated with ultraviolet (UV)/ferrous ions (Fe2+) and peracetic acid (PAA) using fluorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT–ICR MS). The primary reactive species, hydroxyl radicals (·OH) and acylperoxy radicals (CH3C(O)OO·) achieved degradation rates of up to 82.0%, eliminating 84.5% of total fluorescent components and reducing molecular intensity and apparent molecular count by 90.9% and 69.8%, respectively. This treatment significantly reduced the aromaticity of DOM, leading to the formation of more oxidized and stable compounds. Reaction mechanisms indicate that ·OH and CH3C(O)OO· primarily facilitate oxygen addition and dehydrogenation, while CH3C(O)OO· promotes decarboxylation through weak electron transfer processes. The treatment preferentially removes complex DOM containing nitrogen and sulfur heteroatoms, which are key precursors of disinfection byproducts. These findings enhance our understanding of DOM transformations during UV/Fe2+/PAA treatment and provide valuable insights into the safe recycling of SSW.

Mild condition lignin modification enabled high-performance anticorrosive polyurethane coating

The diverse active hydroxyl groups of lignin pose challenges in the preparation of lignin-based polyurethane coatings with exceptional long-term anticorrosive properties. Here, the dense and defect-free lignin-based polyurethane coating with a thickness of 25 ± 5 μm was successfully synthesized using a mild hydroxypropyl lignin modification approach, exhibiting outstanding barrier properties (|Z| > 109 Ω cm2) and long-term anti-corrosion performance exceeding 120 d. Under ambient conditions (i.e., 25 °C and atmospheric pressure), propylene oxide was directly blended with the alkali solution of lignin to effectively convert phenolic hydroxyl groups into more reactive aliphatic hydroxyl groups, while also minimizing the significant increase in molecular weight caused by lignin condensation. As a result, the high crosslinking density of lignin polyurethane coatings effectively prevented the penetration of corrosive media and enhanced the long-term corrosion resistance of the coatings. Overall, the results demonstrate that a mild hydroxypropyl modification process is an effective and facile strategy to prepare highly reactive lignin-based polyols, which is crucial for the development of high-performance bio-based polyurethane anticorrosive coatings.

Bio-Epoxy Resins Based on Lignin and Tannic Acids as Wood Adhesives-Characterization and Bonding Properties.

The possibility of producing and designing bio-epoxides based on the natural polyphenol lignin/epoxidized lignin and tannic acids for application as wood adhesives is presented in this work. Lignin and tannic acids contain numerous reactive hydroxyl phenolic moieties capable of being efficiently involved in the reaction with commercial epoxy resins as a substitute for commercial, non-environmentally friendly, toxic amine-based hardeners. Furthermore, lignin was epoxidized in order to obtain an epoxy lignin that can be a replacement for diglycidyl ether bisphenol A (DGEBA). Cross-linking of bio-epoxy epoxides was investigated via FTIR spectroscopy and their prospects for wood adhesive application were evaluated. This study determined that the curing reaction of epoxy resin can be conducted using lignin/epoxy lignin or tannic acid. Tensile shear strength testing results showed that lignin and tannic acid can effectively replace amine hardeners in epoxy resins. Examination of the failure of the samples showed that all samples had a 100% fracture through the wood. All samples of bio-epoxy adhesives displayed significant tensile shear strength in the range of 5.84-10.87 MPa. This study presents an innovative approach to creating novel cross-linked networks of eco-friendly and high-performance wood bio-adhesives.

Hydroxyl radical-induced C1'-H abstraction reaction of different artificial nucleotides.

Recently, a few antiviral drugs viz Molnupiravir (EIDD-1931), Favipiravir, Ribavirin, Sofosbuvir, Galidesivir, and Remdesivir are shown to be beneficial against COVID-19 disease. These drugs bind to the viral RNA single strand to inhibit the virus genome replication. Similarly, recently, some artificial nucleotides, such as P, J, B, X, Z, V, S, and K were proposed to behave as potent antiviral candidates. However, their activity in the presence of the most reactive hydroxyl (OH) radical is not yet known. Here, the possibility of RNA strand break due to the OH radical-induced C1'-hydrogen (H) abstraction reaction of the above molecules (except Remdesivir) is studied in detail by considering their nucleotide conformation. The results are compared with those of the natural RNA nucleotides (G, C, A, and U). Due to low Gibbs barrier-free energy and high exothermicity,all these nucleotides (except Remdesivir) are prone to OH radical-inducedC1'-H abstraction reaction.As Remdesivir contains a C1'-CN bond,the OH radical substitution reactions at theCN and C1' siteswould likely liberate the catalytically important CN group, thereby downgrading its activity. Initially, the B3LYP-D3 dispersion-corrected density functional theory method and 6-31 + G* basis set were used to optimize all reactant, transition state, and product complexes in the implicit aqueous medium. Subsequently, the structures of these complexes were further optimized by using the ωB97X-D dispersion-corrected density functional theory method and cc-PVTZ basis set in the aqueous medium. The IEFPCM method was used to model the aqueous medium.

High-dose vitamin C as a metabolic treatment of cancer: a new dimension in the era of adjuvant and intensive therapy.

The anti-cancer mechanism of High-dose Vitamin C (HDVC) is mainly to participate in the Fenton reaction, hydroxylation reaction, and epigenetic modification, which leads to the energy crisis, metabolic collapse, and severe peroxidation stress that results in the proliferation inhibition or death of cancer cells. However, the mainstream view is that HDVC does not significantly improve cancer treatment outcomes. In clinical work and scientific research, we found that some drugs or therapies can significantly improve the anti-cancer effects of HDVC, such as PD-1 inhibitors that can increase the anti-cancer effects of cancerous HDVC by nearly three times. Here, the adjuvant and intensive therapy and synergistic mechanisms including HDVC combined applicationof chemoradiotherapies multi-vitamins, targeted drugs, immunotherapies, and oncolytic virus are discussed in detail. Adjuvant and intensive therapy of HDVC can significantly improve the therapeutic effect of HDVC in the metabolic treatment of cancer, but more clinical evidence is needed to support its clinical application.

Degradation of tris(1,3-dichloro-2-propyl) phosphate (TDCPP) by ultraviolet activated hydrogen peroxide: Mechanisms, pathways and toxicity assessments

The ubiquity and ecotoxicity of tri (1,3-dichloro-2-propyl) phosphate (TDCPP) in aquatic environments make it essential to develop efficient related treatment techniques. The present research aims to systematically explore the mechanisms and toxicity changes of TDCPP degradation through UV-driven hydrogen peroxide process (UV/H2O2). The results revealed degradation efficiency of TDCPP attained 95 % with 0.5 mM H2O2, corresponding to a reaction rate constant (k) of 0.04919 min−1. Furthermore, three typical chlorinated OPEs (Cl-OPEs) were simultaneously degraded by the UV/H2O2 process, with different degradation efficiencies, according to the following order: TCEP<TDCPP<TCPP. The degradation efficiency was restricted under alkaline condition and the presence of humic acid (HA), nitrate (NO3–), chloride (Cl-), sulfate (SO42-), and dihydrogen phosphate (H2PO4-). A total of 12 intermediates were identified, which were generated through different pathways, including bond breaking, hydroxylation, and oxidation reactions. The Toxicity Estimation Software Tool (T.E.S.T) results demonstrated stronger mutagenicity and developmental toxicity of the TDCPP intermediates than parent compound. According to RNA sequencing results, UV/H2O2-based TDCPP degradation for 20 min and 60 min still had negative effects on Escherichia coli (E. coli). Indeed, the Gene Ontology (GO) enrichment and Kyoto Encyclopedia of Genes and Genomes (KEGG) analysis results further suggested the stronger negative effect (e.g., damaging effects on the cell membrane, energy metabolism, and vitality) of the 20-min oxidation solution on E. coli, followed by those observed in without treatment and 60-min oxidation solution. Therefore, longer oxidation times are required in the UV/H2O2 process to decrease the toxicity of TDCPP.

Mechanism Exploration of the Photoelectrochemical Immunoassay for the Integration of Radical Generation with Self-Quenching.

Photoelectrochemical (PEC) sensing mechanisms based on enzyme-catalyzed strategies primarily achieve the quantitative analysis of biomolecules through the enhancement or attenuation of photocurrent signals. However, there are still no reports that delve into the principles of photocurrent signaling conversion in the reaction between photoactive materials and the biomolecules. In this work, we demonstrated that indium oxysulfide InOS-0.5 heterojunction has excellent peroxidase activity to catalyze the reaction of H2O2-generated hydroxyl radicals (•OH) with the self-generated electrons, thereby resulting in synergistic quenching of the photocurrent signal. Based on the above principles, we coupled InOS-0.5 with a sandwich-type immunoassay to introduce H2O2 production catalyzed by glucose oxidase for the development of a PEC immunosensing platform. H2O2 reacted with InOS-0.5 to produce •OH with strong oxidizing properties, thus quenching the photogenerated electrons and realizing the PEC detection of the carcinoembryonic antigen (CEA, as a model analyte). The photocurrent intensity decreases with the logarithmic increase in CEA concentration (0.02-50 ng mL-1), with a remarkable limit of detection of 8.9 pg mL-1 (S/N = 3). This study further investigates the mechanism of hydrogen peroxide-induced photocurrent quenching, providing deeper insights into the mechanisms of electron-hole transport in hollow porous semiconductor materials and paving the way for the development of efficient PEC sensors.

Research Progress in Starch-based Dye Adsorbents

Abstract: Starch is a typical environment-friendly biomass material and there are considerable quantities of reactive hydroxyl groups in the starch molecule chain. Modifications could introduce a large number of functional groups, which can bind some dyeing contaminants, thereby removing the dyes. According to the different modification methods, starch-based adsorbents can be divided into three categories that are aminated-modified starch, ionic-modified starch, and composite-modified starch. The preparation method, structure properties, and adsorption capacity of modified starch dye adsorbents have been reviewed in this article. It can be concluded that the adsorption property of adsorbents depends on different adsorption conditions and modification methods. The adsorption properties of the adsorbents have been found to be influenced by temperature, initial concentration of dyes, and pH value of solution. Amination modification can introduce amino or amine groups into the starch skeleton to enhance the chelation or electrostatic effect of the adsorbents on dyes. Ion modification can improve the ion exchange and electrostatic interaction between the adsorbents and the dye. Composite modification can improve specific surface area, pore size, adsorption site, and structural stability of the adsorbents. Future studies are required to focus on producing dye adsorbents with high adsorption performance, stable structure, recyclability, and degradability.

The Reactivity of Hydroxyl Radicals toward Boric Acid as a Function of pH.

Boric acid and its counter-base, borate, are a commonly used buffer pair in many systems where hydroxyl radicals are generated. Boric acid is also used in light water-cooled nuclear reactors to control the excess reactivity of the nuclear fuel. Hydroxyl radicals are generated within the cooling water of the reactor because of intense radiation. The reactivity of the hydroxyl radical toward boric acid has previously been studied, but to the best of our knowledge, only upper limits of the rate constants are available in the literature. In this study, the rate constants for the reaction between the hydroxyl radical and boric acid and its counter-base including several polyborates that form at high boron concentration are determined. The rate constants were determined from competition kinetics using steady-state γ radiolysis and coumarin-3-carboxylic acid as the competing reactant. By varying the pH and accounting for boron speciation, it was possible to determine the rate constant for the different boron species using multilinear regression. The rate constants for boric acid and the counter-base were determined to be 3.6 × 104 and 1.1 × 106 M-1·s-1, respectively, which is very close to the previously determined upper limits of the rate constants. For the polyborate species diborate and tetraborate, the rate constant was determined to be 6.4 × 106 and 6.8 × 106 M-1·s-1, respectively.

Unraveling the Impact of Oxygen Vacancy on Electrochemical Valorization of Polyester Over Spinel Oxides.

Electrochemical upcycling of end-of-life polyethylene terephthalate (PET) using renewable electricity offers a route to generate valuable chemicals while processing plastic wastes. However, it remains a huge challenge to design an electrocatalyst with reliable structure-property relationships for PET valorization. Herein, spinel Co3O4 with rich oxygen vacancies for improved activity toward formic acid (FA) production from PET hydrolysate is reported. Experimental investigations combined with theoretical calculations reveal that incorporation of VO into Co3O4 not only promotes the generation of reactive hydroxyl species (OH*) species at adjacent tetrahedral Co2+ (Co2+ Td), but also induces an electronic structure transition from octahedral Co3+ (Co3+ Oh) to octahedral Co2+ (Co2+ Oh), which typically functions as highly-active catalytic sites for ethylene glycol (EG) chemisorption. Moreover, the enlarged Co-O covalency induced by VO facilitates the electron transfer from EG* to OH* via Co2+ Oh-O-Co2+ Td interaction and the following C─C bond cleavage via direct oxidation with a glyoxal intermediate pathway. As a result, the VO-Co3O4 catalyst exhibits a high half-cell activity for EG oxidation, with a Faradaic efficiency (91%) and productivity (1.02mmol cm-2 h-1) of FA. Lastly, it is demonstrated that hundred gram-scale formate crystals can be produced from the real-world PET bottles via two-electrode electroreforming, with a yield of 82%.

Formate Salt as a Bifunctional Reagent for Hydroxylation and Carbonylation Reactions Under Photochemically Driven Nickel Catalysis.

In this study, we disclose for the first time that formate salt can be used as a bifunctional reagent for the synthesis of phenol derivatives and as a CO source for carbonylative cross-coupling processes using the COware gas reactor under activation free conditions. Key to this success is the in-situ synthesis of aryl formate via an unprecedented nickel/organophotocatalyst system under blue LED irradiation. This developed system demonstrated high applicability to various aryl iodide substrates for synthesizing phenol derivatives. Moreover, the generated CO could be utilized in a range of carbonylative C-heteroatom and C-C processes. Notably, commercially available H13COONa salt can serve as a bifunctional reagent for both synthesizing phenols and generating 13CO.

6‐Hydroxy Picolinohydrazides Promoted Cu(I)‐Catalyzed Hydroxylation Reaction in Water: Machine‐Learning Accelerated Ligands Design and Reaction Optimization

Hydroxylated (hetero)arenes are privileged motifs in natural products, materials, small‐molecule pharmaceuticals and serve as versatile intermediates in synthetic organic chemistry. Herein, we report an efficient Cu(I)/6‐hydroxy picolinohydrazide‐catalyzed hydroxylation reaction of (hetero)aryl halides (Br, Cl) in water. By establishing machine learning (ML) models, the design of ligands and optimization of reaction conditions were effectively accelerated. L32 (6‐HPA‐DMCA) demonstrated high efficiency for (hetero)aryl bromides, promoting hydroxylation reactions with a minimal catalyst loading of 0.01 mol% (100 ppm) at 80 °C to reach 10000 TON or under near‐room temperature conditions for substrates containing sensitive functional groups (3.0 mol%); L42 (6‐HPA‐DTBCA) displayed superior reaction activity for chloride substrates, enabling hydroxylation reactions at 100 °C with 2‐3 mol% catalyst loading. These represent the state of art for both lowest catalyst loading and temperature in the copper‐catalyzed hydroxylation reactions. Furthermore, this method features a sustainable and environmentally friendly solvent system, accommodates a wide range of substrates, and shows potential for developing robust and scalable synthesis processes for key pharmaceutical intermediates.