Single-atom catalysts for the electrochemical reduction of carbon dioxide into hydrocarbons and oxygenates

The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic material and renewable energy-generated electricity drive the conversion of carbon dioxide into high-value chemicals and carbon-neutral fuels.Over the past few years,single-atom catalysts have been intensively studied as they could provide near-unity atom utilization and unique catalytic performance.Single-atom catalysts have become one of the state-of-the-art catalyst materials for the electrochemical reduction of carbon dioxide into carbon monoxide.However,it remains a challenge for single-atom catalysts to facilitate the efficient conversion of carbon dioxide into products beyond carbon monoxide.In this review,we summarize and present important findings and critical insights from studies on the electrochemical carbon dioxide reduction reaction into hydrocarbons and oxygenates using single-atom catalysts.It is hoped that this review gives a thorough recapitulation and analysis of the science behind the catalysis of carbon dioxide into more reduced products through singleatom catalysts so that it can be a guide for future research and development on catalysts with industry-ready performance for the electrochemical reduction of carbon dioxide into high-value chemicals and carbon-neutral fuels.

Research Progress on Removal of Oxygenatesin Fischer-Tropsch Oil by Adsorption

The oxygen-containing compounds in Fischer Tropsch synthetic oil greatly affect the downstream deep processing of hydrocarbons,and effective removal is required.Com-pared to traditional removal technologies such as hydrogenation deoxygenation,solvent extraction,and extraction distillation,adsorption deoxygenation technology has the advantages of low cost,mild operating conditions,easy removal and recovery,and mini-mal impact on oil quality.Therefore,adsorption deoxygenation technology has devel-oped rapidly in various removal processes and has become a research hotspot in the cur-rent Fischer Tropsch oil deoxygenation.Adsorbents are the core of adsorption deoxygen-ation technology.Therefore,this article briefly introduces the adsorption mechanism and summarizes the research progress of adsorbents widely used in recent years,such as silica gel,alumina,molecular sieves,and metal organic frameworks,in adsorbing oxygen-containing compounds in Fischer Tropsch synthetic oils.And provide reference sugges-tions for further adsorption and deoxygenation directions in the future.

Manipulating oxygenate adsorption on N-doped carbon by coupling with CoSn alloy for bifunctional oxygen electrocatalyst

Highly active bifunctional oxygen electrocatalysts accelerate the development of high-performance Zn-air battery,but suffer from the mismatched activities of oxygen evolution reaction(OER)and oxygen reduced reaction(ORR).Herein,highly integrated bifunctional oxygen electrocatalysts,cobalt-tin alloys coated by nitrogen doped carbon(CoSn@NC)are prepared by MOFs-derived method.In this hybrid catalyst,the binary CoSn nanoalloys mainly contribute to highly active OER process while the Co(or Sn)-N-C serves as ORR active sites.Rational interaction between CoSn and NC donates more rapid reaction kinetics than Pt/C(ORR)and IrO_(2)(OER).Such CoSn@NC holds a promise as air-cathode electrocatalyst in Zn-air battery,superior to Pt/C+IrO_(2)catalyst.First-principles calculations predict that CoSn alloys can upgrade charge redistribution on NC and promote the transfer to reactants,thus optimizing the adsorption strength of oxygen-containing intermediates to boost the overall reactivity.The tuning of oxygenate adsorption by interactions between alloy and heteroatom-doped carbon can guide the design of bifunctional oxygen electrocatalysts.

Thrust characteristics of nano-carbon/Al/oxygenated salt nanothermites for micro-energetic applications

Combustion within small motors is key in the application-specific development of nanothermite-based micro-energetic systems. This study evaluates the performance of nanothermite mixtures in a converging-diverging nozzle and an open tube. Mixtures were prepared using nano-aluminum(n-Al),potassium perchlorate(KClO_(4)), and different carbon nanomaterials(CNMs) including graphene-oxide(GO), reduced GO, carbon nanotubes(CNTs) and nanofibers(CNFs). The mixtures were packed at different densities and ignited by laser beam. Performance was measured using thrust measurement,high-speed imaging, and computational fluid dynamics modeling, respectively. Thrust, specific impulse(ISP), volumetric impulse(ISV), as well as normalized energy were found to increase notably with CNM content. Two distinctive reaction regimes(fast and slow) were observed in combustion of low and high packing densities(20% and 55%TMD), respectively. Total impulse(IFT) and ISPwere maximized in the 5%GO/Al/KClO_4 mixture, producing 7.95 m N·s and 135.20 s respectively at 20%TMD, an improvement of 57%compared to a GO-free sample(5.05 m N·s and 85.88 s). CFD analysis of the motors over predicts the thrust generated but trends in nozzle layout and packing density agree with those observed experimentally;peak force was maximized by reducing packing density and using an open tube. The numerical force profiles fit better for the nozzle cases than the open tube scenarios due to the rapid nature of combustion. This study reveals the potential of GO in improving oxygenated salt-based nanothermites,and further demonstrates their applicability for micro-propulsion and micro-energetic applications.

Low-temperature conversion of methane to oxygenates by supported metal catalysts: From nanoparticles to single atoms

Direct cost-effective conversion of abundant methane to high value-added oxygenates(methanol,formic acid,acetic acid,etc.)under mild conditions is prospective for optimizing the structure of energy resources.However,the CAH bond of products is more reactive than that of high thermodynamic stable methane.Exploring an appropriate approach to eliminate the‘‘seesaw effect"between methane conversion and oxygenate selectivity is significant.In this review,we briefly summarize the research progress in the past decade on low-temperature direct conversion of methane to oxygenates in gas-solid-liquid phase over various transition metal(Fe,Cu,Rh,Pd,Au Pd,etc.)based nanoparticle or single-atom catalyst.Furthermore,the prospects of catalyst design and catalysis process are also discussed.

Photocatalytic Synthesis of Hydrocarbon Oxygenates from C_2H_6 and CO_2 over Pd-MoO_3/SiO_2 Catalyst

Pd-MoO3/SiO2 catalyst has been prepared using the method of incipient wetness impregnation. The photo absorbing behaviors and chemisorbing properties of the catalyst have been characterized by UV-vis spectra and TPD-MS experiments. The results indicated that metal Pd loaded on MoOa/SiO2 has a significant effect on the photo absorbing performance of MoOa/SiO2, and an obvious blue shift of the absorption edge is produced. Under UV irradiation, the chemisorption state of CO2 undergoes decomposing process to form CO at 481 K, and a two-site adsorption state of ethane can be formed at around 496 K. Photo-oxidation of ethane using carbon dioxide can mainly produce propanal, ethanol and acetaldehyde in the temperature range of 353-423 K. The presence of metal Pd improves the catalytic activity remarkably.

A Kinetic Study of Selective Hydrogenation of Carbon Monoxide to C_2 Oxygenates on Rh-Mn-Li-Fe/SiO_2 Catalyst

The kinetics of CO hydrogenation for the synthesis of C_2 oxygenates overRh-Mn-Li-Fe/SiO_2 was investigated. Kinetic parameters for the formation of ethanol, acetaldehyde,C'2 oxygenates, methanol and methane were obtained. The activation energy. H_2 and CO dependenceorders for ethanol and acetaldehyde formation differed greatly, the large difference seemed to implythat they were formed through different intermediates.

Influence of extra-framework Al in Fe-MOR catalysts for the direct conversion of methane to oxygenates by nitrous oxide

Iron-containing zeolites play an important role in the selective oxidation of methane to oxygenates by nitrous oxide.A solid-state ion exchange method is adopted to prepare Fe-MOR zeolite catalysts with different amounts of extra-framework Al.EPR spectra and UV-vis spectra show that the percentage of iron ions in tetrahedral or octahedral coordination increases while those of clustered Fe species decrease by the addition of extra-framework Al species.Nitrous oxide titration reveals that more active Fe centers are formed,which promote the nitrous oxide consumption.The number of active centers in the catalyst with the introduction of extra-framework Al is about four times that of the catalyst without the addition of extra-framework Al.Due to this,there is an increase in the methane conversion,total selectivity and yield of oxygenates.

Emergent use of tube tip in pharynx technique in“cannot intubate cannot oxygenate”situation:A case report

BACKGROUND A“cannot intubate,cannot oxygenate(CICO)”situation is a life-threatening condition that requires emergent management to establish a route for oxygenation to prevent oxygen desaturation.In this paper,we describe airway management in a patient with an extended parotid tumor that invaded the airways during CICO using the endotracheal tube tip in the pharynx(TTIP)technique.CASE SUMMARY A 43-year-old man was diagnosed with parotid tumor for>10 years.Computed tomography and nasopharyngeal fiberoptic examination revealed a substantial mass from the right parotid region with a deep extension through the lateral pharyngeal region to the retropharyngeal region and obliteration of the nasopharynx to the oropharynx.Tumor excision was arranged.However,we encountered CICO during anesthesia induction.An endotracheal tube was used as an emergency supraglottic airway device(TTIP)to ventilate the patient in a CICO situation where other tools such as laryngeal mask airway or mask ventilation were not suitable for this complicated and difficult airway.The patient did not experience desaturation despite sudden loss of definite airway.During tracheostomy,the pulse oximetry remained 100%with our technique of ventilating the patient.The arterial blood gas analysis revealed PaCO_(2)35.7 mmHg and PaO2242.5 mmHg upon 50%oxygenation afterward.CONCLUSION Using an endotracheal tube as a supraglottic airway device,patients may have increased survival without experiencing life-threatening desaturation.

Performance of chick pea under the influence of gibberellic acid and oxygenated peptone during germination

The experiments were carried out at the Post Graduate Research Center, to study the influence of Gibberellic Acid (50 ppm) and Oxygenated Peptone (1% aqueous solution) on chick pea (Cicer arietinum L. cv. Vijay) during germination by giving pre-sowing soaking treatment for 6 hours using petriplate method. Both the treatments enhanced the germination process. GA treatment was useful to increase shoot length, mobilization efficiency, emergence index, speed of germination and co-efficient of germination while oxygenated peptone showed an upper hand in root length, shoot/root ratio, biomass and vigour index. GA led to comparatively more synthesis of nucleic acids while oxygenated peptone showed more increase in total carbohydrates and soluble protein content. However, the activity of enzymes like amylase, catalase and protease showed upper hand with oxygenated peptone as compared to GA. In fact GA is costlier and can not be used in organic farming as it enters metabolic pathways of plant and alters them. Hence the use of oxygenated peptone is recommended being less expensive and usable under organic farming condition as it does not enter the plant metabolic pathways and yet brings about significant positive effect.

SEA SURFACE SALINITY AND BOTTOM WATER OXYGENATED CONDITIONS IN WESTERN EQUATORIAL PACIFIC MARGINAL SEAS DURING THE LAST GLACLAL AGE

Based on Core GGC-6 from the South China Sea (SCS) and Core GGC-29 from the Sulu Sea,planktonic and benthic foraminifera and organic carbon measurements were used to evaluate the Water mass conditions in these sea areas during the last glacial age. The results show that the higher organic carbon contents in the SCS and Sulu Sea during the last glacial period were mainly caused by low dissolved oxygen concentrations in bottom waters and that in the last glacial to Holocene, the fluctuation of dissolvd oxygen in the bottom weters was large in the SCS and reatively stable in the Sulu Sea. In addition, increased precipitation reduced surface water salinities, which at the water column to be more stratified in the SCS and Sulu Sea during the last glacial period. This process lowered dissolved oxygen concentrations in bottom waters, which resulted in better preservation of organic matter in both basins.

Direct oxidation of methane to oxygenates over heteropolyanions

Partial oxidation of methane to formaldehyde and methanol was studied at atmospheric pressure in the temperature range of 700-750 °C using heteropolycompound catalysts （NH4）6HSiMo11FeO40, （NH4）4PMo11FeO39, and H4PMo11VO40, which were prepared and characterized by various analysis techniques such as infrared, visible UV, XRD and DTA. O2 or N2O was used as the oxidizing agent, and the principal products of the reaction were CH3OH, CH2O, CO, CO2, and water. The conversion and the selectivity of products depend strongly on the reaction temperature, the nature of oxidizing agent, and the composition of catalyst.

Synergistic Effect of Metal Doping and Tethered Ligand Promoted High-Selectivity Conversion of CO_(2)to C_(2)Oxygenates at Ultra-Low Potential

Effectively controlling the selectivity of C_(2) oxygenates is desirable for electrocatalytic CO_(2) reduction.Copper catalyst has been considered as the most potential for reducing CO_(2) to C_(2) products,but it still suffers from low C_(2) selectivity,high overpotential,and competitive hydrogen evolution reaction(HER).Here,we propose a design strategy to introduce a second metal that weakly binds to H and a functional ligand that provides hydrogen bonds and protons to achieve high selectivity of C_(2)oxygenates and effective suppression of HER on the Cu(100)surface simultaneously.Seven metals and eleven ligands are screened using first-principles calculations,which shows that Sn is the most efficient for inhibiting HER and cysteamine(CYS)ligand is the most significant in reducing the limiting potential of^(*)CO hydrogenation to^(*)CHO.In the post C-C coupling steps,a so-called“pulling effect”that transfers H in the CYS ligand as a viable proton donor to the C_(2)intermediate to form an H bond,can further stabilize the OH group and facilitate the selection of C_(2)products toward oxygenates.Therefore,this heterogeneous electrocatalyst can effectively reduce CO_(2)to ethanol and ethylene glycol with an ultra-low limiting potential of-0.43 V.This study provides a new strategy for effectively improving the selectivity of C_(2)oxygenates and inhibiting HER to achieve advanced electrocatalytic CO_(2)reduction.

Effect of Oxygenates Blending with Gasoline to Improve Fuel Properties

The purpose of this paper is to study the effect of oxygenate additives into gasoline for the improvement of physicochemical properties of blends.Methyl Tertiary Butyl Ether（MTBE）,Methanol,Tertiary butyl alcohol（TBA）,and Tertiary amyl alcohol（TAA） blend into unleaded gasoline with various blended rates of 2.5%,5%,7.5%,10%,15%,and 20%.Physicochemical properties of blends are analyzed by the standard American Society of Testing and Materials（ASTM） methods.Methanol,TBA,and TAA increase density of the mixtures,but MTBE decreases density.The addition of oxygenates lead to a distortion of the base gasoline＇s distillation curves.The Reid vapor pressure（RVP） of gasoline is found to increase with the addition of the oxygenated compounds.All oxygenates improve both motor and research octane numbers.Among these four additives,TBA shows the best fuel properties.

Effect of Blends Gasoline with Oxygenated Additives in the Performance of Internal Combustion Engine

The objective of this study was to evaluate the effect of blends of different oxygenated additives on gasoline in SI engine Otto cycle. The formulations analyzed were: pure gasoline (type A), common gasoline (type C), gasoline type A + 15% (v/v) oxygenated additives (ethanol, ethyl octanoate, ethyl oleate). The experiments were performed using engine Branco 4-stroke and 2-cylinder, electric dynamometer, exhaust system, control unit composed of Multi-K unit, variable selector and load cell, stroboscope tachometer, fuel supply system and stopwatch. The rotation was conserved at 4400 rpm and wheel power varied from 3 kW to 12 kW, with intervals of 3 kW to obtain hourly consumption curves and brake specific fuel consumption. Even esters and ethanol having lower heat of combustion, hourly consumption was similar to pure gasoline (type A). In relation to the brake specific fuel consumption, increasing the wheel power had a better conversion of the mass of fuel burned into energy. Thus, this study showed that the mixture of gasoline and esters (ethyl octanoate and ethyl oleate) presented good efficiency in terms of consumption. This research contributes to the needs and to the current studies in which industries started to add renewable products to petroleum-derived fuels;in order to obtain more sustainable fuels at lower costs.

Quantum Chemical Studies on the Mechanism of Producing Oxygenates in Fischer-Tropsch Synthesis on M/SiO2(M = Ni,Ru,Rh,Pd)

EHMO calculations and orbital analyses of fragment;;have been performed for the formation of oxygenates in Fischer-Tropsch synthesis on the butterfly model for four different metal (Ni,Ru,Rh,Pd) catalysts supported on SiO2.Calculations were made for the four processes,i.e.,CO-dissociation;Coupling of CO and H to produce CHO;Insertion of CO to M-CH3;insertion of CH2 to M-CH3 On the basis of comparing the degree of CO bonds activation and the energy barriers of the foregoing processes for these four catalysts,it is concluded that Ni/SiO2 can be used as the methanation catalyst.On Ru/SiO2 and Rh/SiO2 C2-oxygenated compound can be produced (acetaldehyde),especially Rh/SiO2 is the even better catalyst,and Pd/SiO2 is a methanol synthesis catalyst.

ISOLATION AND STRUCTURE DETERMINATION OF LAMIOPHLOMICL C,A NEW HIGHLY OXYGENATED IRIDOID FROM LAMIOPHLOMIS ROTATA

A new highly oxygenated iridoid,lamiophlomiol C,was isolated from the roots of Lamiophlomis rotata and its structure was elucidated by spectrosoopic techniques and X-ray diffraction.

One-year observation of the mixing states of oxygenated organics-containing single particles in Guangzhou,China

Oxygenated organic molecules(OOMs)play an important role in the formation of secondary organic aerosols(SOAs),but the mixing states of OOMs are still unclear.This study investigates the mixing states of OOM-containing single particles from the measurements taken using a single particle aerosol mass spectrometer in Guangzhou,China in 2022.Generally,the particle counts of OOM particles and the mass concentration of secondary organic carbon(SOC)exhibited similar temporal trends throughout the entire year.The OOM particles were consistently enriched in secondary ions,including 16O−,26CN−,46NO2−,62NO3−,and 97HSO4−.In contrast,the number fractions and diurnal patterns of OOM particles among the total detected particles showed similar distributions in August and October;however,the SOC ratios in fine particulate matter were quite different,suggesting that there were different mixing states of single-particle oxygenated organics.In addition,further classification results indicated that the OOM particles were more aged in October than August,even though the SOC ratios were higher in August.Furthermore,the distribution of hydrocarbon fragments exhibited a notable decrease from January to October,emphasizing the more aged state of the organics in October.In addition,the sharp increase in elemental carbon(EC)-OOM particles in the afternoon in October suggests the potential role of EC in the aging process of organics.Overall,in contrast to the bulk analysis of SOC mass concentration,the mixing states of the OOM particles provide insights into the formation process of SOAs in field studies.