A comprehensive insight into the evolution and molecular structure of basic and neutral nitrogen compounds during the residue hydrotreating(RHT)process was gained through ESI(+)/ESI(-)FT-ICR MS analysis of the feedsto...A comprehensive insight into the evolution and molecular structure of basic and neutral nitrogen compounds during the residue hydrotreating(RHT)process was gained through ESI(+)/ESI(-)FT-ICR MS analysis of the feedstock and its hydrogenated samples,with hydrodenitrogenation(HDN)ratios of 15.9%-70.1%.This study revealed that carbazoles,characterized by a double bond equivalent(DBE)of 9-11,were the refractory neutral nitrogen compounds during the RHT process.Their recalcitrant nature was primarily due to their low aromaticity and high steric hindrance.Conversely,quinolines(DBEs 7 to 9)were the most abundant basic nitrogen compounds.Through a meticulous analysis of DBE evolution,we revealed the intricate reaction mechanisms of benzocarbazoles and dibenzocarbazoles in residual oil,highlighting the crucial role of quinolines as key intermediates in eliminating these compounds.Interestingly,nitrogen compounds with either low or high carbon numbers(for a given DBE)exhibited higher reactivity than those with medium carbon numbers,which can be attributed to the low steric hindrance resulting from short alkyl chains and more naphthenic-aromatic structures,respectively.After hydrotreatment,the molecular structures of the most refractory or abundant nitrogen compounds could consist of two main types:those with multiple naphthenic-aromatic rings and those with long side chains near the nitrogen atom.This research has revealed nitrogen compounds'evolutionary mechanisms and refractory nature,and the molecular structure of the most resistant or abundant basic and neutral nitrogen compounds,providing a deeper understanding of the HDN process and ultimately paving the way for the rational RHT catalyst design and process development.展开更多
Electrochemical nitrogen transformation techniques represent a burgeoning avenue for nitrogen pollutant remediation and synthesizing valuable nitrogenous products from atmospheric nitrogen.Intermetallic compounds(IMCs...Electrochemical nitrogen transformation techniques represent a burgeoning avenue for nitrogen pollutant remediation and synthesizing valuable nitrogenous products from atmospheric nitrogen.Intermetallic compounds(IMCs)nanocrystals,featured with unique geometric,electronic and functional properties,have emerged as promising candidates.The review discusses various synthesis approaches for IMCs,including thermal annealing,wet chemical synthesis,electrochemical synthesis,and other emerging methods,analyzing their advantages and limitations.Then we summarized the recent advances of IMCs in electrocatalytic nitrogen transformation reactions,such as nitrate reduction reaction,nitric oxide reduction reaction,nitrogen reduction reaction,and hydrazine oxidation reaction.Despite significant progress,challenges remain in the field,particularly in adopting more refined strategies to improve catalyst performance and stability.This review aims to comprehensively understand the structural properties of IMCs and their structure-performance relationship,guiding the development of more efficient and stable catalysts for future nitrogen electrochemistry.展开更多
The Ordos Basin is an important intracontinental sedimentary basin in western China for its abundant Mesozoic crude oil resources. The southern part of the Tianhuan Depression is located in the southwestern marginal a...The Ordos Basin is an important intracontinental sedimentary basin in western China for its abundant Mesozoic crude oil resources. The southern part of the Tianhuan Depression is located in the southwestern marginal area of this Basin, in which the Jurassic and Triassic Chang-3 are the main oil-bearing strata. Currently, no consensus has been reached regarding oil source and oil migration in the area, and an assessment of oil accumulation patterns is thus challenging. In this paper, the oil source, migration direction, charging site and migration pathways are investigated through analysis of pyrrolic nitrogen compounds and hydrocarbon biomarkers. Oil source correlations show that the oils trapped in the Jurassic and Chang-3 reservoirs were derived from the Triassic Chang-7 source rocks. The Jurassic and Chang-3 crude oils both underwent distinct vertical migration from deep to shallow strata, indicating that the oils generated by Chang-7 source rocks may have migrated upward to the shallower Chang-3 and Jurassic strata under abnormally high pressures, to accumulate along the sand bodies of the ancient rivers and the unconformity surface. The charging direction of the Jurassic and Chang-3 crude oils is primarily derived from Mubo, Chenhao, and Shangliyuan, which are located northeast of the southern Tianhuan Depression, with oils moving toward the west, southwest, and south. The results show that an integration of biomarker and nitrogen-bearing compound analyses can provide useful information about oil source, migration, and accumulation.展开更多
The sulfides and nitrogen compounds in FCC diesel were analyzed by gas chromatography equipped with a pulsed flame photometric detector(GC-PFPD) and gas chromatography coupled with nitrogen chemiluminescence detection...The sulfides and nitrogen compounds in FCC diesel were analyzed by gas chromatography equipped with a pulsed flame photometric detector(GC-PFPD) and gas chromatography coupled with nitrogen chemiluminescence detection(GC-NCD). And the variation of sulfides and nitrogen compounds in FCC diesel produced from gas oil feed hydrotreated at different temperatures was investigated. The test results showed that two main types of sulfur compounds, i.e. benzothiophenes(BTs) and dibenzothiophenes(DBTs) were found in diesel. Nitrogen compounds are mainly composed of non-basic nitrogen compounds, and indoles and carbazoles account for about 98% of the total nitrogen contents. The sulfides in FCC diesel obtained from hydrotreated feed are mainly BTs with a small amount of 4-MDBT and 4,6-DMDBT. With the increase in FCC feed hydrotreating temperature, indoles content in FCC diesel increases, while carbazoles content decreases.展开更多
The density functional theory(DFT)with dispersion corrections was used to study the adsorption behavior of sulfur and nitrogen compounds on NiMoS phase.The calculations were performed based on a hexagonal cluster mode...The density functional theory(DFT)with dispersion corrections was used to study the adsorption behavior of sulfur and nitrogen compounds on NiMoS phase.The calculations were performed based on a hexagonal cluster model including the Mo-edge,the S-edge,and the rarely mentioned corner site.It was found that the adsorption of quinoline is stronger than that of benzothiophene at all the active sites.It indicated the origin of the inhibition effect of nitrogen compounds on HDS.And Ni atoms located around Mo-edge and corner site exhibit higher adsorption selectivity to sulfur compounds than the nitrogen ones.It means that the increase in Ni-promoting effect may weaken the inhibition effect of nitrogen compounds on HDS.展开更多
The distillation range analysis and elemental analysis of fractioned direct liquefied oil were conducted. Each fraction of liquefied oil contains some nitrogen compounds. Using the acid extraction method and gas chrom...The distillation range analysis and elemental analysis of fractioned direct liquefied oil were conducted. Each fraction of liquefied oil contains some nitrogen compounds. Using the acid extraction method and gas chromatography/mass spectrometry （GC-MS）, the basic nitrogen compounds have been separated and identified. Compared with the nitrogen content of the liquefied oil before and after separation, the basic nitrogen compounds account for more than half of all nitrogen compounds. The basic nitrogen compounds in the light liquefied oil are easily separated, and contain more types of basic nitrogen compounds. The results also show that there are many basic nitrogen compounds in liquefied oil, such as pyrrole, aniline, pyridine, quinoline and so on. However, there are fewer other types of basic nitrogen compounds.展开更多
Metal-organic frameworks(MOFs)have favorable characteristics such as large specific surface area,high porosity,structural diversity,and pore surface modification,giving them great potential for development and attract...Metal-organic frameworks(MOFs)have favorable characteristics such as large specific surface area,high porosity,structural diversity,and pore surface modification,giving them great potential for development and attractive prospects in the research area of modern materials electrocatalysis.However,unsatisfactory catalytic activity and poor electronic conductivity are the main challenges facing MOFs.This review focuses on MOF-based materials used in electrocatalysis,based on the types of catalytic reactions that have used MOF-based materials in recent years along with their applications,and also looks at some new electrocatalytic materials and their future development prospects.展开更多
3,4-Dinitrofurazanfuroxan(DNTF),as a high-energy-density material,features good thermal stability and wide applications.This study aimed to elucidate the thermal decomposition mechanism of DNTF combined with nitrogen-...3,4-Dinitrofurazanfuroxan(DNTF),as a high-energy-density material,features good thermal stability and wide applications.This study aimed to elucidate the thermal decomposition mechanism of DNTF combined with nitrogen-rich compounds containing N-H.The thermal stabilities of DNTF and its hybrid systems were investigated using differential thermal analysis/thermogravimetry(TG),vacuum stability test,and accelerating rate calorimetry under isothermal,non-isothermal,and adiabatic conditions,respectively.Results showed that the thermal stability and thermal safety of DNTF significantly decreased after combining with nitrogen-rich compounds containing N-H.Calculation results showed that the activation energy of the DNTF hybrid systems was significantly lower than that of DNTF.The TGIR was used to monitor the generation of fugitive gases during the thermal decomposition of the DNTF/5-aminotetrazole(5-ATZ)hybrid.Moreover,the nitrogen-rich molecules containing N-H interacted extensively with DNTF,and this interaction accelerated the thermal degradation of DNTF.展开更多
Many nitrogen-containing aromatic compounds （NACs）, such as nitrobenzene （NB）, 4-nitrophenol （4-NP）, aniline （AN）, and 2,4-dinitrophenol （2,4-DNP）, are environmentally hazardous, and their removal from conta...Many nitrogen-containing aromatic compounds （NACs）, such as nitrobenzene （NB）, 4-nitrophenol （4-NP）, aniline （AN）, and 2,4-dinitrophenol （2,4-DNP）, are environmentally hazardous, and their removal from contaminated water is one of the main challenges facing wastewater treatment plants. In this study, synthetic wastewater containing NB, 4-NP, 2,4-DNP, and AN at concentrations ranging from 50 to 180 mg/L was fed into a sequencing batch reactor （SBR）. Analyses of the SBR system indicated that it simultaneously removed more than 99% of the NACs at loading rates of 0.36 kg NB/（m^3·d）, 0.3 kg 4-NP/（m^3·d）, 0.25 kg AN/（m^3·d）, and 0.1 kg 2,4-DNP/（m^3·d）. Bacterial groups of Bacteriodetes, Candidate division TM7, α-Proteobacteria, and β-Proteobacteria were dominant in the clone libraries of 16S rRNA genes retrieved from the microbial communities in the SBR system. ＂Cycle tests＂ designed to alter feeding and aeration parameters of the SBR system demonstrated that the resident microbial biome of the SBR system responded rapidly to changing conditions. Consumption of O2 was concomitant with the apparent mineralization of NACs. Aromatic ring-cleaving dioxygenase activities suggested that （1） AN and NB were degraded via catechol 2,3-dioxygenase; （2） 4-NP was degraded via 1,2,4-benzentriol 1,2-dioxygenase; and （3） 2,4-DNP was degraded via an unresolved pathway.展开更多
The absolute amounts and relative distributions of neutral nitrogen compounds in the Tabei oilfield (e.g. blocks Ln1-Ln11) showed remarkable migration fractionation in the vertical direction. From Ordovician reservoir...The absolute amounts and relative distributions of neutral nitrogen compounds in the Tabei oilfield (e.g. blocks Ln1-Ln11) showed remarkable migration fractionation in the vertical direction. From Ordovician reservoirs (O) to oil legs T-Ⅲ and T-Ⅰ of Triassic reservoirs in blocks LN1-LN11, the concentrations of + decreased from {1.59}μg/g, {0.49}μg/g to {0.17}μg/g (oil). The ratios of various alkylcarbazole isomers, such as 1,8-dimethylcarbazole/nitrogen-partially shielded isomers and 1,8-dimethylcarbazole/nitrogen-exposed isomers, were adopted as the indicators of petroleum migration. The ratios increased from {0.13}, {0.20} to {0.67} and from {0.42}, {0.87} to {3.30}, corresponding to those of Ordovician oil leg and oil legs T-Ⅲ and T-Ⅰ. In going from the south to the north of the Tabei oilfield, the absolute concentrations of neutral nitrogen compounds decreased drastically, and the nitrogen-shielded isomers were enriched relative to nitrogen-exposed isomers and nitrogen-partially shielded isomers. Crude oils in the Tabei oilfield migrated laterally from the Jilake structure to the Sangtamu fault uplift and Lunnan fault uplift, and crude oils in the same fault uplift migrated and remigrated vertically from Ordovician reservoirs, to oil legs T-Ⅲ to T-Ⅰ of Triassic reservoirs.展开更多
The adsorptive denitrogenation from fuels over three metal-organic frameworks(MIL-96(Al),MIL-53(Al)and MIL-101(Cr))was studied by batch adsorption experiments.Four nitrogen-containing compounds(NCCs)pyridine,pyrrole,q...The adsorptive denitrogenation from fuels over three metal-organic frameworks(MIL-96(Al),MIL-53(Al)and MIL-101(Cr))was studied by batch adsorption experiments.Four nitrogen-containing compounds(NCCs)pyridine,pyrrole,quinoline and indole were used as model NCCs in fuels to study the adsorption mechanism.The physicochemical properties of the adsorbents were characterized by XRD,N2physical adsorption,FT-IR spectrum and Hammett indicator method.The metal-organic frameworks(MOFs),especially the MIL-101(Cr)containing Lewis acid sites as well as high specific surface area,can adsorb large quantities of NCCs from fuels.In addition,the adsorptive capacity over MIL-101(Cr)will be different for NCCs with different basicity.The stronger basicity of the NCC is,the more it can be absorbed over MIL-101(Cr).Furthermore,pore size and shape also affect the adsorption capacity for a given adsorbate,which can be proved by the adsorption over MIL-53(Al)and MIL-96(Al).The pseudo-second-order kinetic model and Langmuir equation can be used to describe kinetics and thermodynamics of the adsorption process,respectively.Finally,the regeneration of the used adsorbent has been conducted successfully by just washing it with ethanol.展开更多
Glycine(Gly),cysteine(Cys),aspartic acid(Asp),leucine(Leu),lysine(Lys),and methyl amine(MA) were chosen as typical nitrogenous compounds,and the effects of them on trihalomethanes (THMs) formation and chlorine demand ...Glycine(Gly),cysteine(Cys),aspartic acid(Asp),leucine(Leu),lysine(Lys),and methyl amine(MA) were chosen as typical nitrogenous compounds,and the effects of them on trihalomethanes (THMs) formation and chlorine demand were performed on filtrated water. Results show that the nitrogenous compounds enhance THMs formation,and the increased levels are controlled by characteristics and the concentration of nitrogenous compounds. The increase in THMs formation follows the order of Asp(126 μg/L)>Cys(119 μg/L)>MA(106 μg/L)>Lys(97 μg/L)≈Gly(96 μg/L)>Leu(80 μg/L)(while nitrogenous compounds=1.0 mg/L,and background THMs=60 μg/L). The increase in chlorine demand is approximately proportionate to the content of nitrogenous compounds,which illustrates that the increase is mainly caused by the reaction of nitrogenous compounds with chlorine. And the increase in chlorine demand follows the order of Cys(27.8 mg/L)>Asp(22.6 mg/L)=Gly(22.6 mg/L)>Lys(21.6 mg/L)>MA(14.1 mg/L)>Leu(11.8 mg/L) (while nitrogenous compounds=1.0 mg/L,and background chorine demand=1.8 mg/L). The mechanisms of nitrogenous compounds enhancing THMs formation are summ the increase of chlorine demand raising THMs formation in reaction of NOM with chlorine,and the THMs formation in chlorination of nitrogenous compounds themselves.展开更多
A custom built dynamic oxygen uptake tester was used to study theinfluence of nitrogen compounds on the oxidation characteristics ofthe saturate fractions from mineral base oils. Experimental resultsindicate that nitr...A custom built dynamic oxygen uptake tester was used to study theinfluence of nitrogen compounds on the oxidation characteristics ofthe saturate fractions from mineral base oils. Experimental resultsindicate that nitrogen compounds, especially quinoline and indole,take part in the oxidation of saturates. It is also found that indoleis more active than quinoline. The latter can be oxidized partly intoketoimine, and the former is more rapidly oxidized into acylamide.The oxidation products, ketoimine or acylamide, could inhibit theoxidation of the saturates by decomposing hydroperoxide.展开更多
The nitrogen-containing compounds in Changqing crude oil, its atmospheric residue(AR), and vacuum reside(VR) were characterized by negative and positive ion electrospray ionization(ESI) Fourier transform ion cyclotron...The nitrogen-containing compounds in Changqing crude oil, its atmospheric residue(AR), and vacuum reside(VR) were characterized by negative and positive ion electrospray ionization(ESI) Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS). The heteroatom compounds(N_1, N_2, N_1O_1, O_1, and O_2 class species) could be identified by the negative ESI analysis, while the positive mode could only detect the N_1, N_2, and N_1O_1 class species. Among them, the N_1 class species were found to be predominant in crude oil, as confirmed by either negative or positive ESI analyses,which were similar in composition to AR and VR. These compounds with higher abundance were characterized by double bond equivalent(DBE) values and carbon numbers. The composition of these compounds in crude oil and its AR as well as VR was correlated with their different boiling range, DBE values and carbon numbers. The negative ESI analysis showed that the abundant N_1 class species in crude oil and AR were centered at a DBE value of 12, and these species were likely benzocarbazoles, while the N_1 class species with the DBE value ranging from 13 to 16 having more complicated molecular structures were dominant in VR. And the positive ESI analysis gave the information of the abundant N_1 class species in crude oil, AR, and VR having the DBE values in the range of 10, 9―11, and 10―16, respectively, which were likely the compounds with the core of quinoline and benzoquinoline. The analysis confirmed that the distillation process in refinery preferentially removed the low DBE value and low molecular N-class species and brought them into the light and medium distillates, while those N-class species having a high molecular condensation in the molecules with large carbon number remained in the residual oil and could continually affect the downstream oil refining process.展开更多
Nitrogen-15 isotope-modified compounds are widely used in medicine, pharmacology, agriculture and various fields of science and their nomenclature is gradually increasing. Their widespread use depends on the availabil...Nitrogen-15 isotope-modified compounds are widely used in medicine, pharmacology, agriculture and various fields of science and their nomenclature is gradually increasing. Their widespread use depends on the availability of inexpensive and simple isotope analysis methods. The present article is an attempt to determine the nitrogen-15 isotope content directly in organic compounds without their conversion. The general principle of possibility of determination of the isotopes of nitrogen directly in organic compounds is proposed. Based on the study of mass-spectra of Carbamide Carbonyldiamide, isocyanic acid and nitrobenzene the mass peaks are selected, by which it is possible to determine the atomic fraction of the isotopes of nitrogen. The respective formulas are proposed.展开更多
This paper discussed the direction of secondary migration of oil in the No. 6 area of the Melut Basin by making use of nitrogen compounds as secondary oil migration tracers. From the results, we have found that the oc...This paper discussed the direction of secondary migration of oil in the No. 6 area of the Melut Basin by making use of nitrogen compounds as secondary oil migration tracers. From the results, we have found that the occurrence and compositional characteristics of isomeric-nitrogen compounds in crude oil precisely manifest the fractionation effect of oil migration: with increasing secondary migration distance, the absolute concentrations tend to decrease, and the ratio of nitrogen-shielded isomers to nitrogen-exposed isomers tends to increase. It is considered that the main direction of oil migration in the No. 6 area of the Melut Basin is from north to south.展开更多
Carbazole compounds in crude oils from the Tazhong uplift of the Tarim basin have been fractionated and detected and successfully used to study petroleum migration and trace source rocks in the study area. Alkylcarbaz...Carbazole compounds in crude oils from the Tazhong uplift of the Tarim basin have been fractionated and detected and successfully used to study petroleum migration and trace source rocks in the study area. Alkylcarbazoles have been found in large amounts in the oil samples analyzed and alkylbenzocarbazoles detected in a small concentration only in part of the samples, but alkyldibenzocarbazoles have not been found in oils. Based on the distribution of G1, G2 and G3 of C2-alkylcarbazoles, the ratio of C3-carbazoles to C2-carbazoles and the relative amounts of alkylcarbazoles and alkylbenzocarbazoles, one can know that the vertical oil migration in the Tazhong uplift is generally from below upward, i.e. from the Ordovician through the Silurian to the Carboniferous. Evidently, source rocks in the uplift should be lower Palaeozoic strata (Ordovician and Cambrian). This study shows that carbazoles are of great importance in the study of petroleum migration and source rocks.展开更多
Accurate assessment of organic pollution plays a vital role in environmental protection,administration,and legislation.Methodology involving the evaluation of dichromate-based chemical oxygen demand(COD_(Cr))has been ...Accurate assessment of organic pollution plays a vital role in environmental protection,administration,and legislation.Methodology involving the evaluation of dichromate-based chemical oxygen demand(COD_(Cr))has been widely used for assessing organic pollution in water due to convenience,simplicity,and repeatability.Some nitrogenous organic compounds exhibit very low COD_(Cr)/theoretical oxygen demand(ThOD)ratios,which are termed inoxidizable nitrogenous organic compounds(INOCs)in this study.However,not much attention has been paid to their ubiquitous presence and intrinsic properties.Here,we aimed to determine the under-reporting potential of INOCs when assessing organic water pollution via COD_(Cr) and reveal the mechanisms underlying such under-reporting.COD_(Cr) reported only 0%-20%of the theoretical values of short-chain organic amines and pyridine derivatives,thereby posing severe challenges to both the treatment and reclamation of wastewater.Density functional theory calculations revealed that the use of dichromate-based transformation of INOCs to highly stable protonated/ionic forms under acidic conditions may lead to incomplete reactions,resulting in a significant under-reporting potential of INOCs.Our results may serve as a basis for governments,industries,and other stakeholders to respond more effectively to challenges posed by INOCs.展开更多
To characterize how the speed and load of a medium-duty diesel engine affected the organic compounds in diesel particle matter（PM） below 1 μm, four driving conditions were examined. At all four driving conditions, ...To characterize how the speed and load of a medium-duty diesel engine affected the organic compounds in diesel particle matter（PM） below 1 μm, four driving conditions were examined. At all four driving conditions, concentration of identifiable organic compounds in PM ultrafine（34–94 nm） and accumulation（94–1000 nm） modes ranged from 2.9 to 5.7 μg/m3 and 9.5 to 16.4 μg/m3, respectively. As a function of driving conditions, the non-oxygencontaining organics exhibited a reversed concentration trend to the oxygen-containing organics. The identified organic compounds were classified into eleven classes： alkanes,alkenes, alkynes, aromatic hydrocarbons, carboxylic acids, esters, ketones, alcohols, ethers,nitrogen-containing compounds, and sulfur-containing compounds. At all driving conditions,alkane class consistently showed the highest concentration（8.3 to 18.0 μg/m3） followed by carboxylic acid, esters, ketones and alcohols. Twelve polycyclic aromatic hydrocarbons（PAHs）were identified with a total concentration ranging from 37.9 to 174.8 ng/m3. In addition, nine nitrogen-containing polycyclic aromatic compounds（NPACs） were identified with a total concentration ranging from 7.0 to 10.3 ng/m3. The most abundant PAH（phenanthrene）and NPACs（7,8-benzoquinoline and 3-nitrophenanthrene） comprise a similar molecular（3 aromatic-ring） structure under the highest engine speed and engine load.展开更多
基金the financial support from the National Key Research and Development Program of China(2021YFA1501204)the project of SINOPEC RIPP Co.Ltd(PR20230230)。
文摘A comprehensive insight into the evolution and molecular structure of basic and neutral nitrogen compounds during the residue hydrotreating(RHT)process was gained through ESI(+)/ESI(-)FT-ICR MS analysis of the feedstock and its hydrogenated samples,with hydrodenitrogenation(HDN)ratios of 15.9%-70.1%.This study revealed that carbazoles,characterized by a double bond equivalent(DBE)of 9-11,were the refractory neutral nitrogen compounds during the RHT process.Their recalcitrant nature was primarily due to their low aromaticity and high steric hindrance.Conversely,quinolines(DBEs 7 to 9)were the most abundant basic nitrogen compounds.Through a meticulous analysis of DBE evolution,we revealed the intricate reaction mechanisms of benzocarbazoles and dibenzocarbazoles in residual oil,highlighting the crucial role of quinolines as key intermediates in eliminating these compounds.Interestingly,nitrogen compounds with either low or high carbon numbers(for a given DBE)exhibited higher reactivity than those with medium carbon numbers,which can be attributed to the low steric hindrance resulting from short alkyl chains and more naphthenic-aromatic structures,respectively.After hydrotreatment,the molecular structures of the most refractory or abundant nitrogen compounds could consist of two main types:those with multiple naphthenic-aromatic rings and those with long side chains near the nitrogen atom.This research has revealed nitrogen compounds'evolutionary mechanisms and refractory nature,and the molecular structure of the most resistant or abundant basic and neutral nitrogen compounds,providing a deeper understanding of the HDN process and ultimately paving the way for the rational RHT catalyst design and process development.
基金funded by the National Natural Science Foundation of China(No.22405173)the Shanghai Pujiang Program(No.23PJ1409100)the Project of Overseas Leading Talent of Shanghai.
文摘Electrochemical nitrogen transformation techniques represent a burgeoning avenue for nitrogen pollutant remediation and synthesizing valuable nitrogenous products from atmospheric nitrogen.Intermetallic compounds(IMCs)nanocrystals,featured with unique geometric,electronic and functional properties,have emerged as promising candidates.The review discusses various synthesis approaches for IMCs,including thermal annealing,wet chemical synthesis,electrochemical synthesis,and other emerging methods,analyzing their advantages and limitations.Then we summarized the recent advances of IMCs in electrocatalytic nitrogen transformation reactions,such as nitrate reduction reaction,nitric oxide reduction reaction,nitrogen reduction reaction,and hydrazine oxidation reaction.Despite significant progress,challenges remain in the field,particularly in adopting more refined strategies to improve catalyst performance and stability.This review aims to comprehensively understand the structural properties of IMCs and their structure-performance relationship,guiding the development of more efficient and stable catalysts for future nitrogen electrochemistry.
基金supported by the National Basic Research Program of China (973 Program) (No. 2012CB822003)Specialized Research Fund for the Doctoral Program of Higher Education (No. 20120211110022)the National Science and Technology Major Projects (2011zx05001-004)
文摘The Ordos Basin is an important intracontinental sedimentary basin in western China for its abundant Mesozoic crude oil resources. The southern part of the Tianhuan Depression is located in the southwestern marginal area of this Basin, in which the Jurassic and Triassic Chang-3 are the main oil-bearing strata. Currently, no consensus has been reached regarding oil source and oil migration in the area, and an assessment of oil accumulation patterns is thus challenging. In this paper, the oil source, migration direction, charging site and migration pathways are investigated through analysis of pyrrolic nitrogen compounds and hydrocarbon biomarkers. Oil source correlations show that the oils trapped in the Jurassic and Chang-3 reservoirs were derived from the Triassic Chang-7 source rocks. The Jurassic and Chang-3 crude oils both underwent distinct vertical migration from deep to shallow strata, indicating that the oils generated by Chang-7 source rocks may have migrated upward to the shallower Chang-3 and Jurassic strata under abnormally high pressures, to accumulate along the sand bodies of the ancient rivers and the unconformity surface. The charging direction of the Jurassic and Chang-3 crude oils is primarily derived from Mubo, Chenhao, and Shangliyuan, which are located northeast of the southern Tianhuan Depression, with oils moving toward the west, southwest, and south. The results show that an integration of biomarker and nitrogen-bearing compound analyses can provide useful information about oil source, migration, and accumulation.
文摘The sulfides and nitrogen compounds in FCC diesel were analyzed by gas chromatography equipped with a pulsed flame photometric detector(GC-PFPD) and gas chromatography coupled with nitrogen chemiluminescence detection(GC-NCD). And the variation of sulfides and nitrogen compounds in FCC diesel produced from gas oil feed hydrotreated at different temperatures was investigated. The test results showed that two main types of sulfur compounds, i.e. benzothiophenes(BTs) and dibenzothiophenes(DBTs) were found in diesel. Nitrogen compounds are mainly composed of non-basic nitrogen compounds, and indoles and carbazoles account for about 98% of the total nitrogen contents. The sulfides in FCC diesel obtained from hydrotreated feed are mainly BTs with a small amount of 4-MDBT and 4,6-DMDBT. With the increase in FCC feed hydrotreating temperature, indoles content in FCC diesel increases, while carbazoles content decreases.
基金We gratefully acknowledge the support from the National Key Research and Development Plan(Grant No.2017YFB0306603)China Petrochemical Corporation funding(Sinopec Group,No.117006)on this work.
文摘The density functional theory(DFT)with dispersion corrections was used to study the adsorption behavior of sulfur and nitrogen compounds on NiMoS phase.The calculations were performed based on a hexagonal cluster model including the Mo-edge,the S-edge,and the rarely mentioned corner site.It was found that the adsorption of quinoline is stronger than that of benzothiophene at all the active sites.It indicated the origin of the inhibition effect of nitrogen compounds on HDS.And Ni atoms located around Mo-edge and corner site exhibit higher adsorption selectivity to sulfur compounds than the nitrogen ones.It means that the increase in Ni-promoting effect may weaken the inhibition effect of nitrogen compounds on HDS.
文摘The distillation range analysis and elemental analysis of fractioned direct liquefied oil were conducted. Each fraction of liquefied oil contains some nitrogen compounds. Using the acid extraction method and gas chromatography/mass spectrometry （GC-MS）, the basic nitrogen compounds have been separated and identified. Compared with the nitrogen content of the liquefied oil before and after separation, the basic nitrogen compounds account for more than half of all nitrogen compounds. The basic nitrogen compounds in the light liquefied oil are easily separated, and contain more types of basic nitrogen compounds. The results also show that there are many basic nitrogen compounds in liquefied oil, such as pyrrole, aniline, pyridine, quinoline and so on. However, there are fewer other types of basic nitrogen compounds.
基金financially supported by the National Natural Science Foundation of China(Nos.21677010,51808037)the National Key R&D Program of China(No.2021YFB3500702)the Special Fund of Beijing Key Laboratory of Indoor Air Quality Evaluation and Control(No.BZ0344KF21-04)。
文摘Metal-organic frameworks(MOFs)have favorable characteristics such as large specific surface area,high porosity,structural diversity,and pore surface modification,giving them great potential for development and attractive prospects in the research area of modern materials electrocatalysis.However,unsatisfactory catalytic activity and poor electronic conductivity are the main challenges facing MOFs.This review focuses on MOF-based materials used in electrocatalysis,based on the types of catalytic reactions that have used MOF-based materials in recent years along with their applications,and also looks at some new electrocatalytic materials and their future development prospects.
基金the financially sponsor of the Natural Science Foundation of China(Grant No.51972278)the Outstanding Youth Science and Technology Talents Program of Sichuan(Grant No.19JCQN0085)the Open Project of State Key Laboratory of Environment-friendly Energy Materials(Southwest University of Science and Technology,Grant No.21fksy19)。
文摘3,4-Dinitrofurazanfuroxan(DNTF),as a high-energy-density material,features good thermal stability and wide applications.This study aimed to elucidate the thermal decomposition mechanism of DNTF combined with nitrogen-rich compounds containing N-H.The thermal stabilities of DNTF and its hybrid systems were investigated using differential thermal analysis/thermogravimetry(TG),vacuum stability test,and accelerating rate calorimetry under isothermal,non-isothermal,and adiabatic conditions,respectively.Results showed that the thermal stability and thermal safety of DNTF significantly decreased after combining with nitrogen-rich compounds containing N-H.Calculation results showed that the activation energy of the DNTF hybrid systems was significantly lower than that of DNTF.The TGIR was used to monitor the generation of fugitive gases during the thermal decomposition of the DNTF/5-aminotetrazole(5-ATZ)hybrid.Moreover,the nitrogen-rich molecules containing N-H interacted extensively with DNTF,and this interaction accelerated the thermal degradation of DNTF.
基金Project supported by the Pilot Project of Knowledge Innovation Program of Chinese Academy of Sciences (No. KZCX2-YW-G-009)the National Natural Science Foundation of China (No. 20577067, 30230010).
文摘Many nitrogen-containing aromatic compounds （NACs）, such as nitrobenzene （NB）, 4-nitrophenol （4-NP）, aniline （AN）, and 2,4-dinitrophenol （2,4-DNP）, are environmentally hazardous, and their removal from contaminated water is one of the main challenges facing wastewater treatment plants. In this study, synthetic wastewater containing NB, 4-NP, 2,4-DNP, and AN at concentrations ranging from 50 to 180 mg/L was fed into a sequencing batch reactor （SBR）. Analyses of the SBR system indicated that it simultaneously removed more than 99% of the NACs at loading rates of 0.36 kg NB/（m^3·d）, 0.3 kg 4-NP/（m^3·d）, 0.25 kg AN/（m^3·d）, and 0.1 kg 2,4-DNP/（m^3·d）. Bacterial groups of Bacteriodetes, Candidate division TM7, α-Proteobacteria, and β-Proteobacteria were dominant in the clone libraries of 16S rRNA genes retrieved from the microbial communities in the SBR system. ＂Cycle tests＂ designed to alter feeding and aeration parameters of the SBR system demonstrated that the resident microbial biome of the SBR system responded rapidly to changing conditions. Consumption of O2 was concomitant with the apparent mineralization of NACs. Aromatic ring-cleaving dioxygenase activities suggested that （1） AN and NB were degraded via catechol 2,3-dioxygenase; （2） 4-NP was degraded via 1,2,4-benzentriol 1,2-dioxygenase; and （3） 2,4-DNP was degraded via an unresolved pathway.
文摘The absolute amounts and relative distributions of neutral nitrogen compounds in the Tabei oilfield (e.g. blocks Ln1-Ln11) showed remarkable migration fractionation in the vertical direction. From Ordovician reservoirs (O) to oil legs T-Ⅲ and T-Ⅰ of Triassic reservoirs in blocks LN1-LN11, the concentrations of + decreased from {1.59}μg/g, {0.49}μg/g to {0.17}μg/g (oil). The ratios of various alkylcarbazole isomers, such as 1,8-dimethylcarbazole/nitrogen-partially shielded isomers and 1,8-dimethylcarbazole/nitrogen-exposed isomers, were adopted as the indicators of petroleum migration. The ratios increased from {0.13}, {0.20} to {0.67} and from {0.42}, {0.87} to {3.30}, corresponding to those of Ordovician oil leg and oil legs T-Ⅲ and T-Ⅰ. In going from the south to the north of the Tabei oilfield, the absolute concentrations of neutral nitrogen compounds decreased drastically, and the nitrogen-shielded isomers were enriched relative to nitrogen-exposed isomers and nitrogen-partially shielded isomers. Crude oils in the Tabei oilfield migrated laterally from the Jilake structure to the Sangtamu fault uplift and Lunnan fault uplift, and crude oils in the same fault uplift migrated and remigrated vertically from Ordovician reservoirs, to oil legs T-Ⅲ to T-Ⅰ of Triassic reservoirs.
基金supported by the Program for New Century Excellent Talents in University (NCET-04-0270)National Basic Research Program of China (2011CB201301)
文摘The adsorptive denitrogenation from fuels over three metal-organic frameworks(MIL-96(Al),MIL-53(Al)and MIL-101(Cr))was studied by batch adsorption experiments.Four nitrogen-containing compounds(NCCs)pyridine,pyrrole,quinoline and indole were used as model NCCs in fuels to study the adsorption mechanism.The physicochemical properties of the adsorbents were characterized by XRD,N2physical adsorption,FT-IR spectrum and Hammett indicator method.The metal-organic frameworks(MOFs),especially the MIL-101(Cr)containing Lewis acid sites as well as high specific surface area,can adsorb large quantities of NCCs from fuels.In addition,the adsorptive capacity over MIL-101(Cr)will be different for NCCs with different basicity.The stronger basicity of the NCC is,the more it can be absorbed over MIL-101(Cr).Furthermore,pore size and shape also affect the adsorption capacity for a given adsorbate,which can be proved by the adsorption over MIL-53(Al)and MIL-96(Al).The pseudo-second-order kinetic model and Langmuir equation can be used to describe kinetics and thermodynamics of the adsorption process,respectively.Finally,the regeneration of the used adsorbent has been conducted successfully by just washing it with ethanol.
基金Sponsored by the National Natural Science Foundation of China(Grant No.50908074)the Fundamental Research Funds for the Central Universities(Grant No.2009B17314)
文摘Glycine(Gly),cysteine(Cys),aspartic acid(Asp),leucine(Leu),lysine(Lys),and methyl amine(MA) were chosen as typical nitrogenous compounds,and the effects of them on trihalomethanes (THMs) formation and chlorine demand were performed on filtrated water. Results show that the nitrogenous compounds enhance THMs formation,and the increased levels are controlled by characteristics and the concentration of nitrogenous compounds. The increase in THMs formation follows the order of Asp(126 μg/L)>Cys(119 μg/L)>MA(106 μg/L)>Lys(97 μg/L)≈Gly(96 μg/L)>Leu(80 μg/L)(while nitrogenous compounds=1.0 mg/L,and background THMs=60 μg/L). The increase in chlorine demand is approximately proportionate to the content of nitrogenous compounds,which illustrates that the increase is mainly caused by the reaction of nitrogenous compounds with chlorine. And the increase in chlorine demand follows the order of Cys(27.8 mg/L)>Asp(22.6 mg/L)=Gly(22.6 mg/L)>Lys(21.6 mg/L)>MA(14.1 mg/L)>Leu(11.8 mg/L) (while nitrogenous compounds=1.0 mg/L,and background chorine demand=1.8 mg/L). The mechanisms of nitrogenous compounds enhancing THMs formation are summ the increase of chlorine demand raising THMs formation in reaction of NOM with chlorine,and the THMs formation in chlorination of nitrogenous compounds themselves.
文摘A custom built dynamic oxygen uptake tester was used to study theinfluence of nitrogen compounds on the oxidation characteristics ofthe saturate fractions from mineral base oils. Experimental resultsindicate that nitrogen compounds, especially quinoline and indole,take part in the oxidation of saturates. It is also found that indoleis more active than quinoline. The latter can be oxidized partly intoketoimine, and the former is more rapidly oxidized into acylamide.The oxidation products, ketoimine or acylamide, could inhibit theoxidation of the saturates by decomposing hydroperoxide.
基金supported by the Young Talent Fund of University Association for Science and Technoloqy in Shaanxi, China (No. 20160222)The PetroChina Innovation Foundation (No. 2016D-5007-0404)the Natural Science Basic Research Plan in Shaanxi Province of China (No. 2017JQ2034)
文摘The nitrogen-containing compounds in Changqing crude oil, its atmospheric residue(AR), and vacuum reside(VR) were characterized by negative and positive ion electrospray ionization(ESI) Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS). The heteroatom compounds(N_1, N_2, N_1O_1, O_1, and O_2 class species) could be identified by the negative ESI analysis, while the positive mode could only detect the N_1, N_2, and N_1O_1 class species. Among them, the N_1 class species were found to be predominant in crude oil, as confirmed by either negative or positive ESI analyses,which were similar in composition to AR and VR. These compounds with higher abundance were characterized by double bond equivalent(DBE) values and carbon numbers. The composition of these compounds in crude oil and its AR as well as VR was correlated with their different boiling range, DBE values and carbon numbers. The negative ESI analysis showed that the abundant N_1 class species in crude oil and AR were centered at a DBE value of 12, and these species were likely benzocarbazoles, while the N_1 class species with the DBE value ranging from 13 to 16 having more complicated molecular structures were dominant in VR. And the positive ESI analysis gave the information of the abundant N_1 class species in crude oil, AR, and VR having the DBE values in the range of 10, 9―11, and 10―16, respectively, which were likely the compounds with the core of quinoline and benzoquinoline. The analysis confirmed that the distillation process in refinery preferentially removed the low DBE value and low molecular N-class species and brought them into the light and medium distillates, while those N-class species having a high molecular condensation in the molecules with large carbon number remained in the residual oil and could continually affect the downstream oil refining process.
文摘Nitrogen-15 isotope-modified compounds are widely used in medicine, pharmacology, agriculture and various fields of science and their nomenclature is gradually increasing. Their widespread use depends on the availability of inexpensive and simple isotope analysis methods. The present article is an attempt to determine the nitrogen-15 isotope content directly in organic compounds without their conversion. The general principle of possibility of determination of the isotopes of nitrogen directly in organic compounds is proposed. Based on the study of mass-spectra of Carbamide Carbonyldiamide, isocyanic acid and nitrobenzene the mass peaks are selected, by which it is possible to determine the atomic fraction of the isotopes of nitrogen. The respective formulas are proposed.
文摘This paper discussed the direction of secondary migration of oil in the No. 6 area of the Melut Basin by making use of nitrogen compounds as secondary oil migration tracers. From the results, we have found that the occurrence and compositional characteristics of isomeric-nitrogen compounds in crude oil precisely manifest the fractionation effect of oil migration: with increasing secondary migration distance, the absolute concentrations tend to decrease, and the ratio of nitrogen-shielded isomers to nitrogen-exposed isomers tends to increase. It is considered that the main direction of oil migration in the No. 6 area of the Melut Basin is from north to south.
基金This study was partially supported by the State Educational Commission Foundation for Returned Students.
文摘Carbazole compounds in crude oils from the Tazhong uplift of the Tarim basin have been fractionated and detected and successfully used to study petroleum migration and trace source rocks in the study area. Alkylcarbazoles have been found in large amounts in the oil samples analyzed and alkylbenzocarbazoles detected in a small concentration only in part of the samples, but alkyldibenzocarbazoles have not been found in oils. Based on the distribution of G1, G2 and G3 of C2-alkylcarbazoles, the ratio of C3-carbazoles to C2-carbazoles and the relative amounts of alkylcarbazoles and alkylbenzocarbazoles, one can know that the vertical oil migration in the Tazhong uplift is generally from below upward, i.e. from the Ordovician through the Silurian to the Carboniferous. Evidently, source rocks in the uplift should be lower Palaeozoic strata (Ordovician and Cambrian). This study shows that carbazoles are of great importance in the study of petroleum migration and source rocks.
基金the National Key Research and Development Program of China(2019YFC0408200)for the financial support of the work.
文摘Accurate assessment of organic pollution plays a vital role in environmental protection,administration,and legislation.Methodology involving the evaluation of dichromate-based chemical oxygen demand(COD_(Cr))has been widely used for assessing organic pollution in water due to convenience,simplicity,and repeatability.Some nitrogenous organic compounds exhibit very low COD_(Cr)/theoretical oxygen demand(ThOD)ratios,which are termed inoxidizable nitrogenous organic compounds(INOCs)in this study.However,not much attention has been paid to their ubiquitous presence and intrinsic properties.Here,we aimed to determine the under-reporting potential of INOCs when assessing organic water pollution via COD_(Cr) and reveal the mechanisms underlying such under-reporting.COD_(Cr) reported only 0%-20%of the theoretical values of short-chain organic amines and pyridine derivatives,thereby posing severe challenges to both the treatment and reclamation of wastewater.Density functional theory calculations revealed that the use of dichromate-based transformation of INOCs to highly stable protonated/ionic forms under acidic conditions may lead to incomplete reactions,resulting in a significant under-reporting potential of INOCs.Our results may serve as a basis for governments,industries,and other stakeholders to respond more effectively to challenges posed by INOCs.
基金supported by the Transportation Pollution Research Center, National Institute of Environmental Research in the Republic of Korea and the Korean government overseas study fellowship (Program: 2003-S-20)
文摘To characterize how the speed and load of a medium-duty diesel engine affected the organic compounds in diesel particle matter（PM） below 1 μm, four driving conditions were examined. At all four driving conditions, concentration of identifiable organic compounds in PM ultrafine（34–94 nm） and accumulation（94–1000 nm） modes ranged from 2.9 to 5.7 μg/m3 and 9.5 to 16.4 μg/m3, respectively. As a function of driving conditions, the non-oxygencontaining organics exhibited a reversed concentration trend to the oxygen-containing organics. The identified organic compounds were classified into eleven classes： alkanes,alkenes, alkynes, aromatic hydrocarbons, carboxylic acids, esters, ketones, alcohols, ethers,nitrogen-containing compounds, and sulfur-containing compounds. At all driving conditions,alkane class consistently showed the highest concentration（8.3 to 18.0 μg/m3） followed by carboxylic acid, esters, ketones and alcohols. Twelve polycyclic aromatic hydrocarbons（PAHs）were identified with a total concentration ranging from 37.9 to 174.8 ng/m3. In addition, nine nitrogen-containing polycyclic aromatic compounds（NPACs） were identified with a total concentration ranging from 7.0 to 10.3 ng/m3. The most abundant PAH（phenanthrene）and NPACs（7,8-benzoquinoline and 3-nitrophenanthrene） comprise a similar molecular（3 aromatic-ring） structure under the highest engine speed and engine load.
