Unveiling the chemistry behind the electrolytic production of hydrogen peroxide by oxygenated carbon

Oxygenated carbon materials exhibit outstanding electrocatalytic performance in the production of hydrogen peroxide(H2O2)through a two-electron oxygen reduction reaction.The nature of the active functional group and underlying reaction mechanism,however,remain unclear.Here,a comprehensive workflow was established to identify the active sites from the numerous possible structures.The common hydroxyl group at the notched edge demonstrates a key role in the two-electron process.The local chemical environment weakens the binding of OOH intermediate to substrate while enhancing interaction with solution,thereby promoting the H_(2)O_(2)production.With increasing pH,the intramolecular hydrogen bond between OOH intermediate and hydroxyl decreases,facilitating OOH desorption.Furthermore,the rise in selectivity with increasing potential stems from the suppression of the four-electron process.The active site was further validated through experiments.Guided by theoretical understanding,optimal performance was achieved with high selectivity(>95%)and current density(2.06 mA/cm^(2))in experiment.

Engineering oxygen vacancies on Tb-doped ceria supported Pt catalyst for hydrogen production through steam reforming of long-chain hydrocarbon fuels

Steam reforming of long-chain hydrocarbon fuels for hydrogen production has received great attention for thermal management of the hypersonic vehicle and fuel-cell application.In this work,Pt catalysts supported on CeO_(2)and Tb-doped CeO_(2)were prepared by a precipitation method.The physical structure and chemical properties of the as-prepared catalysts were characterized by powder X-ray diffraction,scanning electron microscopy,transmission electron microscopy,Raman spectroscopy,H_(2)temperature programmed reduction,and X-ray photoelectron spectroscopy.The results show that Tb-doped CeO_(2)supported Pt possesses abundant surface oxygen vacancies,good inhibition of ceria sintering,and strong metal-support interaction compared with CeO_(2)supported Pt.The catalytic performance of hydrogen production via steam reforming of long-chain hydrocarbon fuels(n-dodecane)was tested.Compared with 2Pt/CeO_(2),2Pt/Ce_(0.9)Tb_(0.1)O_(2),and 2Pt/Ce_(0.5)Tb_(0.5)O_(2),the 2Pt/Ce_(0.7)Tb_(0.3)O_(2)has higher activity and stability for hydrogen production,on which the conversion of n-dodecane was maintained at about 53.2%after 600 min reaction under 700℃at liquid space velocity of 9 ml·g^(-1)·h^(-1).2Pt/CeO_(2)rapidly deactivated,the conversion of n-dodecane was reduced to only 41.6%after 600 min.

Marrying luminescent metal nanoclusters to C_(3)N_(4) for efficient photocatalytic hydrogen peroxide production

Photocatalytic oxygen(O_(2))reduction has been considered a promising method for hydrogen peroxide(H_(2)O_(2))production.However,the poor visible light harvesting and low-efficient separation and generation of charge carriers of conventional photocatalysts strongly limited their photocatalytic H_(2)O_(2) generation performance.Herein,we design a highly efficient photocatalyst in this work by marrying luminescent gold-silver nanoclusters(AuAg NCs)to polyethyleneimine(PEI)modified C_(3)N_(4)(C3N4-PEI).The key design in this work is the utilization of highly luminescent AuAg NCs as photosensitizers to promote the generation and separation of charge carriers of C_(3)N_(4)-PEI,thereby ultimately producing abundant e−for O_(2) reduction under visible light illumination(λ≥400 nm).As a result,the as-designed photocatalyst(C3N4-PEI-AuAg NCs)exhibits excellent photocatalytic activity with an H_(2)O_(2) production capability of 82μM in pure water,which is 3.5 times higher than pristine C_(3)N_(4)(23μM).This interesting design provides a paradigm in developing other high-efficient photocatalysts for visible-light-driven H_(2)O_(2) production.

Production of palmitoleic acid by oleaginous yeast Scheffersomyces segobiensis DSM 27193 using systematic dissolved oxygen regulation strategy

Palmitoleic acid(POA)can be naturally found only in few oil seeds and has significant applications in pharmaceutical industry.Recently,the isolated oleaginous yeast Scheffersomyces segobiensis DSM 27193 was identified with high content of POA in its intracellular lipid(13.80%).In this study,process optimization focused on dissolved oxygen regulation to improve POA production was conducted.Dynamic agitation was found to do significant enhancement on POA-rich lipid production than aeration regulation.Under the best condition of 1000 r·min^(-1)of agitation and 1 vvm(airvolume/culture volume/min)of aeration,no ethanol was detected during the whole fermentation process,while a dry biomass concentration of 44.80 g·L^(-1)with 13.43 g·L^(-1)of lipid and 2.93 g·L^(-1)of POA was achieved.Transcription analysis revealed that the ethanol synthetic pathway was downregulated under the condition of high agitation,while the expression of the key enzymes responsible for lipid and POA accumulation were enhanced.

An efficient strategy for photocatalytic hydrogen peroxide production over oxygen-enriched graphitic carbon nitride with sodium phosphate

Photocatalytic hydrogen peroxide(H_(2)O_(2))production is a promising strategy to replace the traditional production processes;however,the inefficient H_(2)O_(2) productivity limits its application.In this study,oxygen-rich g-C_(3)N_(4) with abundant nitrogen vacancies(OCN)was synthesized for photocatalytic H_(2)O_(2) production.X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy indicated that oxygen-containing functional groups(–COOH and C–O–C)were obtained.Electron paramagnetic resonance confirmed the successful introduction of nitrogen vacancies.OCN exhibited efficient photocatalytic H_(2)O_(2) production performance of 1965μmol L^(−1) h^(−1) in air under visible-light irradiation.The high H_(2)O_(2) production was attributed to the enhanced adsorption of oxygen,enlarged specific surface area,and promoted carrier separation.An increased H_(2)O_(2) production rate(5781μmol L^(−1) h^(−1))was achieved in a Na_(3)PO_(4) solution.The improved performance was attributed to the changed reactive oxygen species.Specifically,the adsorbed PO_(4)^(3−) on the surface of the OCN promoted the transfer of holes to the catalyst surface.•O_(2)−obtained by O_(2) reduction reacted with adjacent holes to generate 1O_(2),which could efficiently generate H_(2)O_(2) with isopropanol.Additionally,PO_(4)^(3−),as a stabilizer,inhibited the decomposition of H_(2)O_(2).

Solvothermal fabrication of Bi_(2)MoO_(6) nanocrystals with tunable oxygen vacancies and excellent photocatalytic oxidation performance in quinoline production and antibiotics degradation

Novel Bi_(2)MoO_(6) nanocrystals with tunable oxygen vacancies have been developed via a facile low-cost approach with the assistance of a glyoxal reductant under solvothermal conditions.With the introduction of oxygen vacancies,the optical absorption of Bi_(2)MoO_(6) is extended and its bandgap narrowed.Oxygen vacancies not only lead to the appearance of a defect band level in the forbidden band but can also result in a minor up-shift of the valence band maximum,promoting the mobility of photogenerated holes.Moreover,oxygen vacancies can act as electron acceptors,temporarily capturing electrons excited by light and reducing the recombination of electrons and holes.At the same time,oxygen vacancies help to capture oxygen,which reacts with the captured photogenerated electrons to generate more superoxide radicals(·O_(2)-)to participate in the reaction,thereby significantly promoting the redox performance of the photocatalyst.From Bi_(2)MoO_(6) containing these oxygen vacancies(OVBMO),excellent photocatalytic performance has been obtained for the oxidation of 1,2,3,4-tetrahydroquinoline to produce quinoline and cause antibiotic degradation.The reaction mechanism of the oxidation of 1,2,3,4-tetrahydroquinoline to quinoline over the OVBMO materials is elucidated in terms of heterogeneous Catal.via a radical pathway.

Atomically Dispersed Ruthenium Catalysts with Open Hollow Structure for Lithium-Oxygen Batteries

Lithium–oxygen battery with ultrahigh theoretical energy density is considered a highly competitive next-generation energy storage device,but its practical application is severely hindered by issues such as difficult decomposition of discharge products at present.Here,we have developed N-doped carbon anchored atomically dispersed Ru sites cathode catalyst with open hollow structure(h-RuNC)for Lithium–oxygen battery.On one hand,the abundance of atomically dispersed Ru sites can effectively catalyze the formation and decomposition of discharge products,thereby greatly enhancing the redox kinetics.On the other hand,the open hollow structure not only enhances the mass activity of atomically dispersed Ru sites but also improves the diffusion efficiency of catalytic molecules.Therefore,the excellent activity from atomically dispersed Ru sites and the enhanced diffusion from open hollow structure respectively improve the redox kinetics and cycling stability,ultimately achieving a high-performance lithium–oxygen battery.

The role of reactive oxygen species in gastric cancer

Gastric cancer(GC)ranks fifth in cancer incidence and fourth in cancer-related mortality worldwide.Reactive oxygen species(ROS)are highly oxidative oxygen-derived products that have crucial roles in cell signaling regulation and maintaining internal balance.ROS are closely associated with the occurrence,development,and treatment of GC.This review summarizes recent findings on the sources of ROS and the bidirectional regulatory effects on GC and discusses various treatment modalities for GC that are related to ROS induction.In addition,the regulation of ROS by natural small molecule compounds with the highest potential for development and applications in anti-GC research is summarized.The aim of the review is to accelerate the clinical application of modulating ROS levels as a therapeutic strategy for GC.

Asymmetric configuration activating lattice oxygen via weakening d-p orbital hybridization for efficient C/N separation in urea overall electrolysis

Urea oxidation reaction(UOR)is proposed as an exemplary half-reaction in renewable energy applications because of its low thermodynamical potential.However,challenges persist due to sluggish reaction kinetics and complex by-products separation.To this end,we introduce the lattice oxygen oxidation mechanism(LOM),propelling a novel UOR route using a modified CoFe layered double hydroxide(LDH)catalyst termed CFRO-7.Theoretical calculations and in-situ characterizations highlight the activated lattice oxygen(O_(L))within CFRO-7 as pivotal sites for UOR,optimizing the reaction pathway and accelerating the kinetics.For the urea overall electrolysis application,the LOM route only requires a low voltage of 1.54 V to offer a high current of 100 mA cm^(-2) for long-term utilization(>48 h).Importantly,the by-product NCO^(-)−is significantly suppressed,while the CO_(2)2/N_(2) separation is efficiently achieved.This work proposed a pioneering paradigm,invoking the LOM pathway in urea electrolysis to expedite reaction dynamics and enhance product selectivity.

Rational design of vitamin C/defective carbon van der Waals heterostructure for enhanced activity,durability and storage stability toward oxygen reduction reaction

Metal-free defective carbon materials with abundant active sites have been widely studied as low-cost and efficient oxygen reduction reaction(ORR)electrocatalysts in metal-air batteries.However,the active sites in defective carbon are easily subjected to serious oxidation or hydroxylation during ORR or storage,leading to rapid degradation of activity.Herein,we design a van der Waals heterostructure comprised of vitamin C(VC)and defective carbon(DC)to not only boost the activity but also enhance the durability and storage stability of the DC-VC electrocatalyst.The formation of VC van der Waals between DC and VC is demonstrated to be an effective strategy to protect the defect active sites from oxidation and hydroxylation degradation,thus significantly enhancing the electrochemical durability and storage anti-aging performance.Moreover,the DC-VC van der Waals can reduce the reaction energy barrier to facilitate the ORR.These findings are also confirmed by operando Fourier transform infrared spectroscopy and density functional theory calculations.It is necessary to mention that the preparation of this DC-VC electrocatalyst can be scaled up,and the ORR performance of the largely produced electrocatalyst is demonstrated to be very consistent.Furthermore,the DC-VC-based aluminum-air batteries display very competitive power density with good performance maintenance.

Targeting oxidative stress with natural products: A novel strategy for esophageal cancer therapy

Esophageal cancer(ESC)is a malignant tumor that originates from the mucosal epithelium of the esophagus and is part of the digestive tract.Although the exact pathogenesis of ESC has not been fully elucidated,excessive oxidative stress is an important characteristic that leads to the development of many cancers.Abnormal expression of several proteins and transcription factors contributes to oxidative stress in ESCs,which alters the growth and proliferation of ESCs and promotes their metastasis.Natural compounds,including alkaloids,terpenes,polyphenols,and xanthine compounds,can inhibit reactive oxygen species production in ESCs.These compounds reduce oxidative stress levels and subsequently inhibit the oc-currence and progression of ESC through the regulation of targets and pathways such as the cytokine interleukins 6 and 10,superoxide dismutase,the NF-+ACY-kappa+ADs-B/MAPK pathway,and the mammalian Nrf2/ARE target pathway.Thus,targeting tumor oxidative stress has become a key focus in anti-ESC therapy.This review discusses the potential of Natural products(NPs)for treating ESCs and summarizes the application prospects of oxidative stress as a new target for ESC treatment.The findings of this review provide a reference for drug development targeting ESCs.Nonetheless,further high-quality studies will be necessary to determine the clinical efficacy of these various NPs.

Modified TiO_(2)/In_(2)O_(3) heterojunction with efficient charge separation for visible-light-driven photocatalytic CO_(2) reduction to C_(2) product

Utilizing sunlight to convert CO_(2) into chemical fuels could address the greenhouse effect and fossil fuel crisis,Heterojunction structure catalysts with oxygen vacancy are attractive in the field of photocatalytic CO_(2) conversion.Herein,a modified TiO_(2)/In_(2)O_(3)(R-P2 5/In_(2)O_(3-x)) type Ⅱ heterojunction composite with oxygen vacancies is designed for photocatalytic CO_(2) reduction,which exhibits excellent CO_(2) reduction activity,with a C_(2) selectivity of 56.66%(in terms of R_(electron)).In situ Fourier-transform infrared spectroscopy(DRIFTS) and time-resolved photoluminescence(TR-PL) spectroscopy are used to reveal the intermediate formation of the photocatalytic mechanism and photogenerated electron lifetime,respectively.The experimental characterizations reveal that the R-P25/In_(2)O_(3-x) composite shows a remarkable behavior for coupling C-C bonds.Besides,efficient charge separation contributes to the improved CO_(2) conversion performance of photocatalysts.This work introduces a type Ⅱ heterojunction composite photocatalyst,which promotes understanding the CO_(2) reduction mechanisms on heterojunction composites and is valuable for the development of photocatalysts.

Natural product-induced oxidative stress-synergistic anti-tumor effects of chemotherapeutic agents

Reactive oxygen species are closely related to tumor development.In recent years,reactive oxygen species has become a hot spot in tumor therapy,and many natural substances in nature contain compound components with anti-tumor effects.However,there is a lack of discussion on the synergistic anti-tumor effects of natural products in combination with chemotherapeutic drugs through reactive oxygen species.The terms“natural products”,“reactive oxygen species”,“anti-tumor”,and“chemotherapy”were used to identify the synergistic effects of natural products.We conducted a systematic literature search in PubMed and Web of Science databases for relevant research articles and reviews published in recent years.We systematically summarized the studies related to anti-tumor active ingredients in natural compounds in the field of reactive oxygen species in recent years.A total of 77 relevant literatures were included.Among them,45 literatures containing various natural products such as terpenoids,flavonoids,alkaloids,etc.exert anti-tumor effects by regulating reactive oxygen species levels,and 32 literatures regarding adjunctive role of natural products in anti-tumor therapy.In this study,we found that natural products exert anti-tumor effects by elevating reactive oxygen species levels.It provides strong theoretical support for future clinical studies.

Regulatory role of peroxynitrite in advanced glycation end products mediated diabetic cardiovascular complications

The Advanced Glycation End Products(AGE)binding with its receptor can increase reactive oxygen species(ROS)generation through specific signaling mediators.The effect of superoxide(O2-)and O2-mediated ROS and reactive nitrogen species depends on their concentration and location of formation.Nitric oxide(NO)has anti-inflammatory and anticoagulant properties and a vasodilation effect,but NO can be deactivated by reacting with O_(2)^(-).This reaction between NO and O2-produces the potent oxidant ONOO−.Therefore,ONOO-'s regulatory role in AGEs in diabetic cardiovascular complications must considered as a regulator of cardiovascular complications in diabetes.

Using triple oxygen isotopes and oxygen-argon ratio to quantify ecosystem production in the mixed layer of northern South China Sea slope region

Quantifying the gross and net production is an essential component of carbon cycling and marine ecosystem studies.Triple oxygen isotope measurements and the O_(2)/Ar ratio are powerful indices in quantifying the gross primary production and net community production of the mixed layer zone,respectively.Although there is a substantial advantage in refining the gas exchange term and water column vertical mixing calibration,application of mixed layer depth history to the gas exchange term and its contribution to reducing indices error are unclear.Therefore,two cruises were conducted in the slope regions of the northern South China Sea in October 2014(autumn)and June 2015(spring).Discrete water samples at Station L07 in the upper 150 m depth were collected for the determination ofδ^(17)0,δ^(18)O,and the O_(2)/Ar ratio of dissolved gases.Gross oxygen production(GOP)was estimated using the triple oxygen isotopes of the dissolved O_(2),and net oxygen production(NOP)was calculated using O_(2)/Ar ratio and O_(2)concentration.The vertical mixing effect in NOP was calibrated via a N_(2)O based approach.GOP for autumn and spring was(169±23)mmol/(m^(2)·d)(by O_(2))and(189±26)mmol/(m^(2)·d)(by O_(2)),respectively.While NOP was 1.5 mmol/(m^(2)·d)(by O_(2))in autumn and 8.2 mmol/(m^(2)·d)(by O_(2))in spring.Application of mixed layer depth history in the gas flux parametrization reduced up to 9.5%error in the GOP and NOP estimations.A comparison with an independent O_(2)budget calculation in the diel observation indicated a26%overestimation in the current GOP,likely due to the vertical mixing effect.Both GOP and NOP in June were higher than those in October.Potential explanations for this include the occurrence of an eddy process in June,which may have exerted a submesoscale upwelling at the sampling station,and also the markedly higher terrestrial impact in June.

3-36 Effect of Oxygen on the Cellulase Production of Aspergillus niger

Lignocellulosic biomass is the most abundant organic raw material in the world. Due to its complexity, lignocellulosebioconversion requires the action of multiple enzymes. The complete hydrolysis of cellulose requires theaction of the cellulase system containing cellobiohydrolase, endoglucanase and -glucosidase[1]. Aspergillus spp:produce all three enzyme activities of the cellulase complex and exhibit strong hydrolytic activity towards cellulose,and Aspergillus niger has been mainly used for -glucosidase production[2]. Aspergillus niger is a kind of aerobicmicroorganisms, but there is little oxygen when it is used to silage for degrading the feed cellulose and enhancingthe feed's palatability. The aim of this study is to evaluate the influence of oxygen on the growth and cellulaseproduction of Aspergillus niger.

The Effect of Toxic Sulfide Exposure on Oxygen Consumption and Oxidation Products in Urechis unicinctus(Echiura:Urechidae)

To investigate sulfide detoxification in Urech＆ unicinctus, oxygen consumption rate and sulfide detoxification products were analyzed during sulfide exposure under controlled laboratory conditions. The results showed that oxygen consumption rates were elevated significantly during 3 h sulfide exposure compared to the control （P〈0.05）. The concentration of sulfite in body wall and hindgut of experimental worms increased significantly （P〈0.05） when exposed to 50 μmolL^-1 sulfide, reached a maximum at 24 h and then decreased. Similar result was observed in worms exposed to 150 μmolL^-1 sulfide except that sulfite concentration reached a maximum at 12 h. Contents of thiosulfate in body wall and hindgut of U. unicinctus exposed to sulfide were also significantly higher than that of the control without sulfide exposure. In conclusion, during short-time sulfide exposure U. unicinctus may raise oxygen consumption to detoxify toxic sulfide into sulfite and thiosulfate. Sulfide detoxification was restrained when the exposure time was prolonged or sulfide concentration was increased, which was indicated by decrease of sulfite, the intermediate product of sulfide detoxification.

Effect of calcination temperatures on photocatalytic H_(2)O_(2)-production activity of ZnO nanorods

Photocatalytic hydrogen peroxide(H_(2)O_(2))production from O_(2) and H2O is an ideal process for solar‐to‐chemical energy conversion.Herein,ZnO nanorods are prepared via a simple hydrothermal method for photocatalytic H_(2)O_(2) production.The ZnO nanorods exhibit varied performance with different calcination temperatures.Benefiting from calcination,the separation efficiency of photo‐induced carriers is significantly improved,leading to the superior photocatalytic activity for H_(2)O_(2) production.The H_(2)O_(2) produced by ZnO calcined at 300℃ is 285μmol L^(−1),which is over 5 times larger than that produced by untreated ZnO.This work provides an insight into photocatalytic H2O2 production mechanism by ZnO nanorods,and presents a promising strategy to H2O2 production.

Recent progress in production and usage of hydrogen peroxide

Hydrogen peroxide has attracted increasing interest as an environmentally benign and green oxidant that can also be used as a solar fuel in fuel cells.This review focuses on recent progress in production of hydrogen peroxide by solar-light-driven oxidation of water by dioxygen and its usage as a green oxidant and fuel.The photocatalytic production of hydrogen peroxide is made possible by combining the e^(-)and 4e-oxidation of water with the e^(-)reduction of dioxygen using solar energy.The catalytic control of the selectivity of the e^(-)vs.4e-oxidation of water is discussed together with the selectivity of the e^(-)vs.4e-reduction of dioxygen.The combination of the photocatalytic e^(-)oxidation of water and the e^(-)reduction of dioxygen provides the best efficiency because both processes afford hydrogen peroxide.The solar-light-driven hydrogen peroxide production by oxidation of water and by reduction of dioxygen is combined with the catalytic oxidation of substrates with hydrogen peroxides,in which dioxygen is used as the greenest oxidant.

Efficient hydrogen production through the chemical looping redox cycle of YSZ supported iron oxides

The chemical looping process,where an oxygen carrier is reduced and oxidized in a cyclic manner,offers a promising option for hydrogen production through splitting water because of the much higher water splitting efficiency than solar electrocatalytic and photocatalytic process.A typical oxygen carrier has to comprise a significant amount of inert support,to maintain stability in multiple redox cycles,thereby resulting in a trade-off between the reaction reactivity and stability.Herein,we proposed the use of ion-conductive yttria-stabilized zirconia(YSZ)support Fe_(2)O_(3)to prepare oxygen carriers materials.The obtained Fe_(2)O_(3)/YSZ composites showed high reactivity and stability.Particularly,Fe_(2)O_(3)/YSZ-20(oxygen storage capacity,24.13%)exhibited high hydrogen yield of~10.30 mmol g^(-1) and hydrogen production rate of~0.66 mmol g^(-1) min^(-1) which was twice as high as that of Fe_(2)O_(3)/Al_(2)O_(3).Further,the transient pulse test indicated that active oxygen diffusion was the ratelimiting step during the redox process.The electrochemical impedance spectroscopy(EIS)measurement revealed that the YSZ support addition facilitated oxygen diffusion of materials,which contributed to the improved hydrogen production performance.The support effect obtained in this work provides a potentially efficient route for the modification of oxygen carrier materials.