CO_(2)reformation of methane(CRM)and CO_(2)methanation are two interconnected processes with significant implications for greenhouse gas reduction and sustainable energy production for industrial purposes.While Nibase...CO_(2)reformation of methane(CRM)and CO_(2)methanation are two interconnected processes with significant implications for greenhouse gas reduction and sustainable energy production for industrial purposes.While Nibased catalysis suffers from poor stability due to coke formation or sintering,we report a super stable remedy.The active sites of mesoporous MgO were loaded using wet impregnation.The incorporation of Ni and promoters altered the physical features of the catalysts.Sm–Ni/MgO showed the smallest crystallite size,specific surface area,and pore volume.The Sm–Ni/MgO catalyst was selected as the most suitable candidate for CRM,with 82%CH4 and H2/CO ratio of approximately 100%and also for CO_(2)methanation with the conversion of carbon dioxide(82%)and the selectivity toward methane reaches 100%at temperatures above 300ᵒC.Furthermore,the Sm–Ni/MgO catalyst was stable for 900 min of continuous reaction,without significant carbon deposition.This stability was largely due to the high oxygen mobility on the catalyst surface in the presence of Sm.Overall,we demonstrated the efficacy of using promoted Ni catalysts supported by mesoporous magnesia for the improved reformation of greenhouse gases.展开更多
Rational design is important to achieve high-performance sorbents used to remove the contaminants of emerging concern(CECs) from water.However, it is hard to propose effective design guidelines due to the lack of a cl...Rational design is important to achieve high-performance sorbents used to remove the contaminants of emerging concern(CECs) from water.However, it is hard to propose effective design guidelines due to the lack of a clear understanding of the interaction mechanisms. By means of systematic quantum chemical computations, as a case study, we investigated the interactions between zeolite X/M^(n+)-zeolite X(Si/Al=1,M^(n+)=Cu^(2+) and Ni^(2+)) and three commonly used CECs(namely salicylic acid, carbamazepine and ciprofloxacin) in water to clarify the adsorption mechanisms. Our computations found that anionic salicylic acid cannot be adsorbed by neither zeolite X nor M^(n+)-zeolite X in neutral water due to the high electrostatic repulsion. In comparison, carbamazepine and ciprofloxacin have favorable binding energies with both zeolite X and M^(n+)-zeolite X, and their interactions with M^(n+)-zeolite X are stronger due to the joint effects of H-bond, metal complexation and electrostatic interaction. The adsorption loading of ciprofloxacin, which has a large molecular size, on M^(n+)-zeolite X is limited due to the steric hindrance. In general, steric hindrance, electrostatic interaction, H-bond and metal complexation are dominant factors for the examined systems in this study. Thus, for the design of high-performance absorbing materials, we should fully consider the molecular properties of pollutants(molecular size, surface electrostatic potential and atomic type, etc.), and properly enhance the favorable effects and avoid the unfavorable factors as much as possible under the guidance of the interaction mechanisms.展开更多
The distribution of organic compounds in stored lipids affects their migration,transformation,bioaccumulation,and toxicity in organisms.The storage lipid/water distribution coefficient(log K_(lip/w))of organic chemica...The distribution of organic compounds in stored lipids affects their migration,transformation,bioaccumulation,and toxicity in organisms.The storage lipid/water distribution coefficient(log K_(lip/w))of organic chemicals,which quantitatively determines such distribution,has become a key parameter to assist their ecological security and health risk.Due to the impossibility to measure K_(lip/w)values for a huge amount of chemicals,it is necessary to develop predictive approaches.In this work,a quantitative structure-property relationship(QSPR)model for estimating log K_(lip/w)values of small organic compounds was constructed based on 305 experimental log K_(lip/w)values.Quantum chemical descriptors and n-octanol/water partitioning coefficient were employed to characterize the intermolecular interactions that dominate log K_(lip/w)values.The hydrophobic and electrostatic interactions and molecular size have been found to play important roles in governing the distribution of chemicals between lipids and aqueous phases.The regression(R2=0.959)and validation(Q2=0.960)results indicate good fitting performance and robustness of the developed model.A comparison with the predictive performance of other commercial software further proves the higher accuracy and stronger predictive ability of the developed K_(lip/w)predictive model.Thus,it can be used to predict the K_(lip/w)values of cycloalkanes,long-chain alkanes,halides(with fluorine,chlorine,and bromine as substituents),esters(without phosphate groups),alcohols(without methoxy groups),and aromatic compounds.展开更多
基金supports rendered by Zhejiang Normal University(Grant No.YS304221928)Iran National Science Foundation.No.:4002219Yonsei University Mirae Campus.
文摘CO_(2)reformation of methane(CRM)and CO_(2)methanation are two interconnected processes with significant implications for greenhouse gas reduction and sustainable energy production for industrial purposes.While Nibased catalysis suffers from poor stability due to coke formation or sintering,we report a super stable remedy.The active sites of mesoporous MgO were loaded using wet impregnation.The incorporation of Ni and promoters altered the physical features of the catalysts.Sm–Ni/MgO showed the smallest crystallite size,specific surface area,and pore volume.The Sm–Ni/MgO catalyst was selected as the most suitable candidate for CRM,with 82%CH4 and H2/CO ratio of approximately 100%and also for CO_(2)methanation with the conversion of carbon dioxide(82%)and the selectivity toward methane reaches 100%at temperatures above 300ᵒC.Furthermore,the Sm–Ni/MgO catalyst was stable for 900 min of continuous reaction,without significant carbon deposition.This stability was largely due to the high oxygen mobility on the catalyst surface in the presence of Sm.Overall,we demonstrated the efficacy of using promoted Ni catalysts supported by mesoporous magnesia for the improved reformation of greenhouse gases.
基金the Postdoctoral Fellowships Program from the NSF-sponsored Puerto Rico Institute for Functional Nanomaterials under Grant EPS-1002410support from NSF CREST Phase 2 Grant HRD-1345156
文摘Rational design is important to achieve high-performance sorbents used to remove the contaminants of emerging concern(CECs) from water.However, it is hard to propose effective design guidelines due to the lack of a clear understanding of the interaction mechanisms. By means of systematic quantum chemical computations, as a case study, we investigated the interactions between zeolite X/M^(n+)-zeolite X(Si/Al=1,M^(n+)=Cu^(2+) and Ni^(2+)) and three commonly used CECs(namely salicylic acid, carbamazepine and ciprofloxacin) in water to clarify the adsorption mechanisms. Our computations found that anionic salicylic acid cannot be adsorbed by neither zeolite X nor M^(n+)-zeolite X in neutral water due to the high electrostatic repulsion. In comparison, carbamazepine and ciprofloxacin have favorable binding energies with both zeolite X and M^(n+)-zeolite X, and their interactions with M^(n+)-zeolite X are stronger due to the joint effects of H-bond, metal complexation and electrostatic interaction. The adsorption loading of ciprofloxacin, which has a large molecular size, on M^(n+)-zeolite X is limited due to the steric hindrance. In general, steric hindrance, electrostatic interaction, H-bond and metal complexation are dominant factors for the examined systems in this study. Thus, for the design of high-performance absorbing materials, we should fully consider the molecular properties of pollutants(molecular size, surface electrostatic potential and atomic type, etc.), and properly enhance the favorable effects and avoid the unfavorable factors as much as possible under the guidance of the interaction mechanisms.
基金financially supported by the National Natural Science Foundation of China(Nos.21707122 and 21677133)National College Students Innovation and Entrepreneurship Training Program(No.202010345069)。
文摘The distribution of organic compounds in stored lipids affects their migration,transformation,bioaccumulation,and toxicity in organisms.The storage lipid/water distribution coefficient(log K_(lip/w))of organic chemicals,which quantitatively determines such distribution,has become a key parameter to assist their ecological security and health risk.Due to the impossibility to measure K_(lip/w)values for a huge amount of chemicals,it is necessary to develop predictive approaches.In this work,a quantitative structure-property relationship(QSPR)model for estimating log K_(lip/w)values of small organic compounds was constructed based on 305 experimental log K_(lip/w)values.Quantum chemical descriptors and n-octanol/water partitioning coefficient were employed to characterize the intermolecular interactions that dominate log K_(lip/w)values.The hydrophobic and electrostatic interactions and molecular size have been found to play important roles in governing the distribution of chemicals between lipids and aqueous phases.The regression(R2=0.959)and validation(Q2=0.960)results indicate good fitting performance and robustness of the developed model.A comparison with the predictive performance of other commercial software further proves the higher accuracy and stronger predictive ability of the developed K_(lip/w)predictive model.Thus,it can be used to predict the K_(lip/w)values of cycloalkanes,long-chain alkanes,halides(with fluorine,chlorine,and bromine as substituents),esters(without phosphate groups),alcohols(without methoxy groups),and aromatic compounds.
基金supported by the National Major Scientific Research Instrument Development Project of the National Natural Science Foundation of China(21827801)the National Natural Science Foundation of China(22171235)。
