Benzyl Alcohol Research Articles

Exposure to potentially harmful excipients in medications among neonates at a state hospital in Malaysia

Objectives This study aimed to determine the incidence, types and predictors of Potentially Harmful Excipients (PHE) exposure among hospitalized neonates. Methods A prospective observational study was conducted from March to April 2022 in neonatal wards at a state hospital in Malaysia. The PHEs of interest were aspartame, benzalkonium chloride, benzyl alcohol, benzoic acid or benzoates, ethanol, parabens, polysorbate 80, propylene glycol, saccharin sodium, sorbitol and sulfites. Product information leaflets (PILs) and summaries of product characteristics (SPCs) were referred to obtain information on active pharmaceutical ingredient, strength, trade name as well as type and amount of the excipients. Results A total of 108 neonates were recruited and 97.2% of them were exposed to at least one PHE. Parabens (47.2%) and sulfites (27.5%) were the two most commonly administered PHEs. Benzyl alcohol is contraindicated in neonates but was administered to 8% of neonates in this study. The median daily dose of ethanol (24.11 mg/kg/day, IQR 19.73, 28.49) exceeded the acceptable daily intake (ADI) by four times. However, the dose was not available for all PHEs as this information is not always available in the PIL or SPC. Administration of cardiovascular drugs was associated with a higher risk of exposure to any PHE (OR 6.38, CI 2.75, 14.79, p-value < 0.001). Conclusion The exposure of PHE among neonates in this study is high with certain PHEs exceeding the ADI. It highlights the need for certain strategies to be implemented to reduce such exposure in neonates.

P–ρ–T Data and Derived Volumetric Properties of Benzyl Alcohol, ±2-Octanol (Racemic Mixture), and 1-Heptanol from 283.15 to 363.15 K at Pressures up to 65 MPa

<i>P</i>–ρ–<i>T</i> Data and Derived Volumetric Properties of Benzyl Alcohol, ±2-Octanol (Racemic Mixture), and 1-Heptanol from 283.15 to 363.15 K at Pressures up to 65 MPa

Nitridated Nickel Mesh as Industrial Water and Alcohol Oxidation Catalyst: Reconstruction and Iron‐Incorporation Matters

AbstractNickel mesh (NM) is used in industrial alkaline water electrolyzers due to its cost‐effectiveness and conductivity. However, the decisive factors that advance the efficiency and sustainability of such electrodes are only partially understood. Herein, an efficient NM‐based electrocatalyst for the oxygen evolution reaction is developed via a single‐step nitridation route on a commercially used NM substrate and sheds light on the role of reconstruction and iron content to boost catalyst performance and durability. Remarkably, the activated Ni3N/NM catalyst required an overpotential of 0.46 V to deliver 1 A cm−2 in ambient conditions (1 M KOH, 25 °C). This overpotential decreases substantially to 0.28 V in industrially relevant conditions (6 M KOH, 85 °C) and is maintained for 235 h. Ni3N/NM partially transformed into NiFe layered (oxy)hydroxide in both conditions, while the active structure's Fe content is reconstruction condition dependent (temperature and KOH concentration). Electrodes reconstructed under industrially relevant conditions performed better than ambient reconstructed ones due to a more pronounced iron‐incorporation from KOH and the evolution of porous morphologies. In industrial environments, activated Ni3N/NM excels in selectively converting benzyl alcohol to benzoic acid, achieving an impressive yield of 96%.

Synthesis of Stilbenes by Cyanide/Base-Mediated Coupling of Benzylic Chlorides and Alcohols

AbstractA straightforward procedure has been developed for the direct synthesis of stilbenes from benzylic chlorides and alcohols. The transformation employs a two-step one-pot protocol where the benzylic chloride is first subjected to a substitution with potassium cyanide in o-xylene. Without workup, the resulting arylacetonitrile is then reacted directly with the benzylic alcohol and potassium tert-butoxide to generate the stilbene framework. The condensation has been performed with a variety of commercially available benzylic chlorides and alcohols to afford substituted stilbenes as the pure E-isomers. A kinetic isotope effect of 5.2 has been measured for the overall transformation when comparing benzyl alcohol and α,α-d 2-benzyl alcohol. The release of cyanide during the final elimination to stilbene has been confirmed by a picrate test. Thus, the potassium tert-butoxide-mediated elimination of cyanide is believed to proceed by an E1cB mechanism where the deprotonation reaction constitutes the rate-determining step.

Hydrogen-Induced Formation of Surface Acid Sites on Pt/Al(PO3)3 Enables Remarkably Efficient Hydrogenolysis of C-O Bonds in Alcohols and Ethers.

The hydrogenolysis of oxygenates such as alcohols and ethers is central to the biomass valorization and also a valuable transformation in organic synthesis. However, a mild and efficient catalyst system for the hydrogenolysis of a large variety of alcohols and ethers with various functional groups is still underdeveloped. Here, we report an aluminum metaphosphate-supported Pt nanoparticles (Pt/Al(PO3)3) for the hydrogenolysis of a wide variety of primary, secondary, and tertiary alkyl and benzylic alcohols, and dialkyl, aryl alkyl, and diaryl ethers, including biomass-derived furanic compounds, under mild conditions (0.1-1 atm of H2, as low as 70 °C). Mechanistic studies suggested that H2 induces formation of the surface Brønsted acid sites via its cleavage by supported Pt nanoparticles. Accordingly, the high efficiency and the wide applicability of the catalyst system are attributed to the activation and cleavage of C-O bonds by the hydrogen-induced Brønsted acid sites with the assistance of Lewis acidic Al sites on the catalyst surface. The high efficiency of the catalyst implies its potential application in energy-efficient biomass valorization or fine chemical synthesis.

New Cu(II) Schiff-base complex modified on magnetic nanoparticles: Oxidation and DFT investigation

A copper magnetic nanocatalyst was facilely synthesized by surface modification of silica magnetic nanoparticles (Fe3O4@SiO2) via reaction with 3-aminopropyltrimethoxysilane (Fe3O4@SiO2@APTMS), followed by a subsequent reaction with thiophene-2-carbaldehyde to form a Schiff base (Fe3O4@SiO2@SB). Sequentially, reaction with Cu(CH3COO)2·H2O in ethanol yielded Fe3O4@SiO2@[SB@Cu] (CH3COO)2. This nanomagnetic catalyst was comprehensively characterized using Fourier Transform Infrared Spectroscopy (FT-IR), X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Thermogravimetric Analysis (TGA), and Vibrating Sample Magnetometry (VSM) techniques. The catalytic proficiency of these nanoparticles was evaluated through alkene and alcohol oxidation reactions. Under optimized conditions, the nanocatalyst exhibited significant efficacy in oxidizing styrene, cyclohexene, and benzyl alcohol, with notable selectivity values of 88 %, 100 %, and 100 % for the respective formation of styrene epoxide, 2-cyclohexene-1-one, and benzoic acid. The heterogeneous copper nanocatalyst offers advantages, including high conversion rates, facile separation, and exceptional selectivity in alkene and alcohol oxidation. Additionally, this study investigated density functional theory (DFT) methods, encompassing geometric optimization, natural charge analysis, molecular electrostatic potential maps, and vibrational normal modes of the chelating ligands.

Hydrogen‐Induced Formation of Surface Acid Sites on Pt/Al(PO3)3 Enables Remarkably Efficient Hydrogenolysis of C−O Bonds in Alcohols and Ethers

AbstractThe hydrogenolysis of oxygenates such as alcohols and ethers is central to the biomass valorization and also a valuable transformation in organic synthesis. However, a mild and efficient catalyst system for the hydrogenolysis of a large variety of alcohols and ethers with various functional groups is still underdeveloped. Here, we report an aluminum metaphosphate‐supported Pt nanoparticles (Pt/Al(PO3)3) for the hydrogenolysis of a wide variety of primary, secondary, and tertiary alkyl and benzylic alcohols, and dialkyl, aryl alkyl, and diaryl ethers, including biomass‐derived furanic compounds, under mild conditions (0.1–1 atm of H2, as low as 70 °C). Mechanistic studies suggested that H2 induces formation of the surface Brønsted acid sites via its cleavage by supported Pt nanoparticles. Accordingly, the high efficiency and the wide applicability of the catalyst system are attributed to the activation and cleavage of C−O bonds by the hydrogen‐induced Brønsted acid sites with the assistance of Lewis acidic Al sites on the catalyst surface. The high efficiency of the catalyst implies its potential application in energy‐efficient biomass valorization or fine chemical synthesis.

Synthesis of β‐Aryl‐α,β‐Dehydroaminophosphonates by Pd‐Catalyzed Fujiwara–Moritani C−C Coupling

AbstractThe treatment of diethyl α,β‐dehydroaminophosphonate 1 with various arenes (ArH=toluene 2 a, benzene 2 b, anisole 2 c, bromobenzene 2 d, chlorobenzene 2 e, benzyl alcohol 2 f, p‐xylene 2 g) in acetic acid (AcOH) at 120 °C for 8 h in the presence of Pd(OAc)2 (10 % mol, OAc=acetate) and AgOAc (3.4 equivalents) results in the formation of the corresponding β‐aryl derivatives E‐Ar(H)C=C(NHAc)P(O)(OEt)2 3 a–3 g. The reaction proceeds through double C−H activation (arene and alkene) and subsequent C−C oxidative coupling (Fujiwara–Moritani reaction), processes catalyzed by Pd and assisted by Ag. The obtained products 3 a–3 g are isosteric analogs of phenylalanine and are obtained with high selectivity. Thus, geometrical E‐isomers have been obtained in all studied cases, however mixtures of ortho‐/meta‐/para‐isomers are observed when the activated position in the starting arene 2 is considered.

Co doping induced phase transition and its distinct effects on the catalytic performance of MnO2 toward toluene oxidation

Manganese oxides are very important and conventional catalysts that have demonstrated appreciable catalytic activity for the oxidation of volatile organic compounds (VOCs). Nevertheless, pure manganese oxides suffer from poor activity especially at low temperatures, making it difficult to meet industrial applications. In this work, Co species were successfully doped into the lattice of MnO2 aiming at constructing defects to boost its catalytic performance for VOCs oxidation. In combination with the results of systematic characterizations, we found that Co doping forced the catalyst to transform from α‐MnO2 to spinel phase (Co,Mn)(Co,Mn)2O4. During this process, the metal–oxygen bonds are significantly weakened, which induces the massive generation of oxygen defects, endowing the Co modified catalysts with enhanced redox property and improved ability to adsorb and activate gaseous oxygen. As a result, Co doped catalysts show much better catalytic activity compared with pristine α‐MnO2, among which Mn10Co10 exhibits the best performance showing a decrease of 41°C and 51°C in T50 and T90 compared with the raw sample, respectively. Furthermore, Mn10Co10 demonstrates excellent stability, water resistance, and reusability, illustrating a great potential for industrial applications. Moreover, path of toluene decomposition over Co10Mn10 was revealed by in situ DRIFTS experiment, which complies with the sequence of toluene → benzyl alcohol → benzaldehyde → benzoate → maleic anhydride → CO2 and H2O.

Boosting photocatalytic hydrogen peroxide evolution through aerobic oxidative dehydrogenation of benzyl alcohol over amino acid hyper-cross-linked polymer in two-phase system

The fusion of photocatalytic hydrogen peroxide (H2O2) production with the generation of high-value organic compounds carries the potential to optimize the utilization of solar energy. The efficient generation and separation of products constitute indispensable elements in constructing a proficient reaction system. Herein, the photocatalytic production of H2O2 via the aerobic oxidative dehydrogenation of benzyl alcohol (BA) was realized through the application of an amino acid hyper-cross-linked polymer (H6P-HCPs) in two-phase system. The outcomes unveiled that the H6P-HCPs with 1:6 M ratio of L-phenylalanine (L-Phe) and hexaphenylbenzene (HPB) achieves the highest generation rate of H2O2 (29.26 mmol∙gcat-1∙h-1), stoichiometric amount of benzyl alcohol oxidation products were obtained as 96% benzaldehyde (23.94 mmol∙gcat-1∙h-1) and 4% benzoic acid (5.56 mmol∙gcat-1∙h-1). Time-dependent density functional theory (TDDFT) calculations illuminated that the presence of L-Phe monomers of H6P-HCPs not only facilitated electron transfer from L-Phe to HPB, capitalizing on electronegativity differentials, but also instigated the formation of O2•- while concurrently adjusting its hydrophobic nature. These factors, in concert, were instrumental in the accomplishment of this highly efficient photocatalytic process.

Data retrieval from archival renal biopsies using nonlinear microscopy.

Thorough examination of renal biopsies may improve understanding of renal disease. Imaging of renal biopsies with fluorescence nonlinear microscopy (NLM) and optical clearing enables three-dimensional (3D) visualization of pathology without microtome sectioning. Archival renal paraffin blocks from 12 patients were deparaffinized and stained with Hoechst and Eosin for fluorescent nuclear and cytoplasmic/stromal contrast, then optically cleared using benzyl alcohol benzyl benzoate (BABB). NLM images of entire biopsy fragments (thickness range 88-660 μm) were acquired using NLM with fluorescent signals mapped to an H&E color scale. Cysts, glomeruli, exudative lesions, and Kimmelstiel-Wilson nodules were segmented in 3D and their volumes, diameters, and percent composition could be obtained. The glomerular count on 3D NLM volumes was high indicating that archival blocks could be a vast tissue resource to enable larger-scale retrospective studies. Rapid optical clearing and NLM imaging enables more thorough biopsy examination and is a promising technique for analysis of archival paraffin blocks.

Perfluorinated Zinc Porphyrin Sensitized Photoelectrosynthetic Cells for Enhanced TEMPO-Mediated Benzyl Alcohol Oxidation.

This research introduces a novel series of perfluorinated Zn(II) porphyrins with positive oxidation potentials designed as sensitizers for photoelectrosynthetic cells, with a focus on promoting the oxidation of benzyl alcohol (BzOH) mediated by the 2,2,6,6-tetramethyl-1-piperidine N-oxyl (TEMPO) organocatalyst. Three dyes, CLICK-3, CLICK-4, and BETA-4, are meticulously designed to explore the impact of substituents and their positions on the perfluorinated porphyrin ring in terms of redox potentials and energy level alignment when coupled with SnO2/TiO2-based photoanodes and TEMPO mediator. A comprehensive analysis utilizing spectroscopy, electrochemistry, photophysics, and computational techniques of the dyes in solution and sensitized thin films unveils an enhanced charge-separation character in the 4D-π-1A type BETA-4. Incorporating four dimethylamino donor groups at the periphery of the porphyrin ring and a BTD-accepting linker at the β-pyrrolic position equips the structure with a more efficient donor-acceptor system. This enhancement ensures improved light-harvesting capacity, resulting in a doubled incident photon-to-current conversion efficiency (IPCE% ≃30%) in the presence of LiI compared to meso-substituted dyes CLICK-3 and CLICK-4. Sensitizing SnO2/TiO2 thin films with BETA-4 successfully promotes the photooxidation of benzyl alcohol (BzOH) in the presence of the rapid TEMPO radical catalyst, yielding photocurrents of approximately 125 μA/cm2 in an optimized TBPy/LiClO4/ACN electrolyte. Notably, when lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) replaces TBPy as the base for TEMPO-catalyzed BzOH oxidation, a remarkable photocurrent of around 800 μA/cm2 is achieved, marking one of the highest values reported for this photoelectrochemical reaction to date. This study underscores that the proper functionalization of perfluorinated zinc porphyrins positions these dyes as ideal candidates for sensitizing SnO2/TiO2 in the photodriven oxidation of BzOH. It also highlights the crucial role of carefully tuning electrolyte composition based on the electronic properties of molecular sensitizers.

Mesoporous Si-WO3-supported Pt catalysts with high catalytic performance and excellent water resistance for toluene oxidation

Reducing emissions of volatile organic compounds (VOCs) is an integral part of improving the quality of the atmospheric environment. Catalytic oxidation has become an effective means of treating low and medium concentration VOCs exhausts due to its advantages in terms of removal efficiency, energy saving and environmental protection. Due to the unique inherent properties of supported precious metal catalysts, they show good catalytic efficiency in VOCs emission reduction. In this study, the mesoporous Si-WO3 support was first synthesized by the P123-assisted sol-gel method, and the xPt/Si-WO3 catalysts with the actual loadings (x = 0.19, 0.48, and 0.81 wt%) of Pt nanoparticles (NPs) were then obtained, physicochemical properties of these materials were characterized using a variety of techniques, and their catalytic activities and water resistance for the oxidation of toluene were evaluated. The results showed that Pt NPs with an average particle size of 2.3−3.3 nm were highly dispersed on the mesoporous Si-WO3 support, and the 0.81Pt/Si-WO3 sample exhibited the highest catalytic activity for toluene oxidation at a space velocity of 20,000 mL/(g h) (T50% = 167 °C and T90% = 180 °C; specific reaction rate at 160 °C = 8.54 µmol/(gPt s), turnover frequency (TOFPt) at 160 °C = 1.67 × 10−3 s−1, and apparent activation energy = 45 kJ/mol). The good catalytic performance of 0.81Pt/Si-WO3 was associated with its large surface area, well dispersed Pt NPs, high adsorbed oxygen species concentration, large toluene adsorption capacity, and strong interaction between Pt NPs and mesoporous Si-WO3. The 0.81Pt/Si-WO3 sample possessed excellent water resistance, and the introduction of 5 vol% or 10 vol% water vapor to the reaction system enhanced toluene oxidation since part of water vapor participated in the oxidation of toluene. In addition, the toluene oxidation pathway might obey the sequence of (adsorbed toluene + adsorbed oxygen species) → benzyl alcohol → (benzoic acid and benzaldehyde) → maleic anhydride → (carbon dioxide and water).

Effect of carbon oxygen functionalization on the activity of Pd/C catalysts in hydrogenation reactions

AbstractThis paper presents a study on the effects of oxygen functionalities on a mesoporous and graphitized carbon support (GNP, Graphene Nanoplatelets), on the catalytic activity of Pd/GNP catalysts in hydrogenation reactions. A functionalization method in liquid phase has been employed, using different oxidants (HNO3, H2O2, KMnO4), with the aim to tune the amount and the type of introduced oxygen functionalities. Preformed Pd nanoparticles have been used as Pd‐precursor to limit differences in metal particle size and dispersion on differently functionalized carbon. The catalytic behaviour in benzaldehyde hydrogenation/hydrogenolysis to benzyl alcohol and toluene revealed that the introduction of oxygen functionalities has a generally detrimental effect. NMR relaxometry studies highlighted the weaker interaction between the carbonyl group and the functionalized Pd/GNP surface than the non–functionalized Pd/GNP demonstrating that the origin of the different catalytic activity lies on the first step of the reaction. O‐functionalities also impacted on the Pd0/Pd2+ ratio at the surface which is an established parameter correlated to the reaction rate.

Simultaneous determination of four non paraben preservatives (benzyl alcohol, phenoxyethanol, sodium benzoate, and salicylic acid) in shampoos by an isocratic HPLC method

Salicylic acid (SA), sodium benzoate (SB), phenoxyethanol (PO), and benzyl alcohol (BA) are “non paraben” preservatives commonly used in cosmetic products like shampoos, and often in combination of at least two compounds to assure their antimicrobial effectiveness at low concentrations. In this study, an HPLC-DAD method was developed and validated for simultaneous determination of SA, SB, PO, and BA in commercial shampoos. The method was carried out using an YMC Triart C18 (250 × 4.6 mm, 5 µm) column with a mixture of methanol and 0.02 M solution of phosphate buffer pH 2.7 (35 : 65, v/v) as mobile phase. The flow rate of mobile phase was maintained at 1.0 mL per minute, the injection volume was 20 µL and the UV detection was done at 208 nm for BA and at 230 nm for SA, SB and PO. The method was fully validated according to requirements on analytical method performance of AOAC International and validation results confirmed its reliability and suitability for intended application. The method was employed to determine the four “non paraben” preservatives in 18 commercial shampoos, finding the actual content of these substances in all samples conformed to their regulatory limits.

KOtBu Mediated Alcohol Dehydrogenation Strategy: Synthesis of 2‐Aryl Quinazolinones

AbstractHerein we report an atom‐economical, transition metal‐free method for synthesizing 2‐aryl quinazolinones through a cascade annulation of 2‐amino benzamide and benzyl alcohol. The reaction proceeds via KOtBu‐mediated acceptorless alcohol dehydrogenation pathways. The procedure tolerates a wide variety of functional groups and provides a convenient method for the synthesis of 2‐aryl quinazolinones. Mechanistic insights by experiments and DFT calculations lead to unveil the reaction mechanism.

Dihalosalicylaldehyde based molybdenum(VI) complexes: Synthesis, spectral characterization, crystal structures, and catalytic activities for the selective oxidation of benzylic alcohols

Three ONO donor Schiff base ligands were obtained by the condensation of 3,5-dihalosalicylaldehydes with nicotinoylhydrazide (H2Cl2SN: (E)-N'-(3,5-dichlorosalicylaldehyde) nicotinoylhydrazone, H2Br2SN: (E)-N'-(3,5-dibromosalicylaldehyde) nicotinoylhydrazone, and H2I2SN: (E)-N'-(3,5-diiodosalicylaldehyde) nicotinoylhydrazone on refluxing in ethanol. The treatment of [MoO2(acac)2] (acac = acetylacetonato) with these ligands in methanol afforded cis-dioxidomolybdenum(VI) complexes [MoO2(Cl2SN)(CH3OH)] (1), [MoO2(Br2SN)(CH3OH)] (2), and [MoO2(I2SN)(CH3OH)] (3). Various techniques like NMR (1H and 13C), FT-IR, Mass, TGA, elemental (CHN), and single-crystal X-ray diffraction analysis (for H2Cl2SN·H2O, 2a, [MoO2(Br2SN)(C2H5OH)], and 3a, [MoO2(I2SN)(H2O)].DMF) were utilized to characterize the synthesized compounds. The data collected from diffraction studies revealed that the geometry around Mo(VI) ions was distorted octahedral. Additionally, all complexes were successfully screened as catalysts for the selective oxidation of benzylic alcohols employing ethanol and hydrogen peroxide.

The aggregation behaviors of organic radicals in polar fluorinated arenes

AbstractPolar fluorinated arenes can promote organic free radical reactions, which have attracted scientists’ interest in recent years. However, it is still unknown how these solvents interact weakly with organic radical molecules to influence their reactivity. In this study, we investigated how organic free radicals aggregate in five polar fluorocarbon solvents, and demonstrated that different substituents can influence their aggregation behaviors. In these solvents, small organic radicals with simple substituents maintain a homogeneous solution; however, radicals with substituents that form intermolecular hydrogen bonds or with long‐chain aliphatic hydrocarbons tend to aggregate in them, whereas substituents of long‐chain aliphatic hydrocarbons tend to promote aggregation better. The critical aggregation concentrations of these aggregates are measured by concentration‐dependent UV–visible spectroscopy. Their topological morphologies are all spherical based on TEM. The compactness and rotational motivation speed of radical molecules within these aggregates are determined by EPR spectroscopy. The particle sizes of these aggregates are determined by analyzing their cyclic voltammograms. Most excitingly, electrochemical experiments reveal that the aggregation behaviors of free radical molecules with intermolecular hydrogen bonds can significantly increase their catalytic rate for electro‐oxidizing benzyl alcohol in such a solvent. The results of this study indicate that in polar fluorinated arenes organic radical molecules’ aggregation behaviors are related to their structures. This may provide guidelines for regulating organic radical reactivity in these solvents in the future.

Radical-driven selective oxidation of benzyl alcohol on MnCoOx catalysts with no oxidant other than air in reactor

Mn reinforced Co3O4 catalysts (MnCoOx) were prepared by a facile solid phase mixed foaming method with an in-situ heating enhancement for the formation of spinel phase mixed oxide species, and studied in the selective oxidation of benzyl alcohol just the air in reactor as oxygen donor. It was found that the MnCoOx catalysts are composed of relatively minimal spinel MnCo2O4 mixed oxide and massive Co3O4 to form MnCo2O4-Co3O4 oxide pair. The micro-domains of MnCo2O4-Co3O4 oxide pair present two redox couples of Mn3+/Mn2+ and Co3+/Co2+ instead of the single one of Co3+/Co2+ in Co3O4, and then dramatically enhance the formation of superoxide radicals (•O2–) species from the O2 in air, which can efficiently initiate the conversion of benzyl alcohol to benzaldehyde in a Fenton-like processes. With no oxidant other than air in reactor, the interaction between MnCo2O4 and Co3O4 in MnCoOx catalysts leads to a benzyl alcohol conversion up to 98 % with a 100 % benzaldehyde selectivity at atmospheric pressure while single component Co3O4 can only present a benzyl alcohol conversion at 37 %. This embodiment of highly efficient heterogeneous selective oxidation just with air as oxidant provides a probability for developing a low-cost and super-facile radical-induced selective oxidation process for alcohols.

Microscopic-Level Insights into P-O-Induced Strong Electronic Coupling Over Nickel Phosphide with Efficient Benzyl Alcohol Electrooxidation.

Electrooxidation of biomass into fine chemicals coupled with energy-saving hydrogen production for a zero-carbon economy holds great promise. Advanced anode catalysts determine the cell voltage and electrocatalytic efficiency greatly, further the rational design and optimization of their active site coordination remains a challenge. Herein, a phosphorus-oxygen terminals-rich species (Ni2P-O-300) via an anion-assisted pyrolysis strategy is reported to induce strong electronic coupling and high valence state of active nickel sites over nickel phosphide. This ultimately facilitates the rapid yet in-situ formation of high-valence nickel with a high reaction activity under electrochemical conditions, and exhibits a low potential of 1.33V vs. RHE at 10mAcm-2, exceeding most of reported transition metal-based catalysts. Advanced spectroscopy, theoretical calculations, and experiments reveal that the functional P-O species can induce the favorable local bonding configurations for electronic coupling, promoting the electron transfer from Ni to P and the adsorption of benzyl alcohol (BA). Finally, the hydrogen production efficiency and kinetic constant of BA electrooxidation by Ni2P-O-300 are increased by 9- and 2.8- fold compared with the phosphorus-oxygen terminals-deficient catalysts (Ni2P-O-500). This provides an anion-assisted pyrolysis strategy to modulate the electronic environment of the Ni site, enabling a guideline for Ni-based energy/catalysis systems.