The cobalt precursor affects the catalytic performance of Co/SiO_2 catalyst remarkably. The catalyst prepared from cobalt acetate exhibits excellent activity, stability and resistance to carbon deposition.
An investigation was made using a continuous fixed bed reactor to understand the influence of carbon deposition obtained under different conditions on CH_(4)-CO_(2)reforming.Thermogravimetry(TG)and X-ray diffraction(X...An investigation was made using a continuous fixed bed reactor to understand the influence of carbon deposition obtained under different conditions on CH_(4)-CO_(2)reforming.Thermogravimetry(TG)and X-ray diffraction(XRD)were employed to study the characteristics of carbon deposition.It was found that the carbonaceous catalyst is an efficient catalyst in methane decomposition and CH_(4)-CO_(2)reforming.The trend of methane decomposition at lower temperatures is similar to that at higher temperatures.The methane conversion is high during the initial of stage of the reaction,and then decays to a relatively fixed value after about 30 min.With temperature increase,the methane decomposition rate increases quickly.The reaction temperature has significant influence on methane decomposition,whereas the carbon deposition does not affect methane decomposition significantly.Different types of carbon deposition were formed at different methane decomposition reaction temperatures.The carbon deposition Type I generated at 900℃ has a minor effect on CH_(4)-CO_(2)reforming and it easily reacts with carbon dioxide,but the carbon deposition Type II generated at 1000℃and 1100℃clearly inhibits CH_(4)-CO_(2)reforming and it is difficult to react with carbon dioxide.The results of XRD showed that some graphite structures were found in carbon deposition Type II.展开更多
A kind of new catalyst-carbonaceous catalyst-for CH_(4)-CO_(2) reformation has been developed in our laboratory.The effect of both oxygen-bearing functional group such as phenolic hydroxyl,carbonyl,carboxyl,and lacton...A kind of new catalyst-carbonaceous catalyst-for CH_(4)-CO_(2) reformation has been developed in our laboratory.The effect of both oxygen-bearing functional group such as phenolic hydroxyl,carbonyl,carboxyl,and lactonic,and ash such as Fe_(2)O_(3),Na_(2)CO_(3),and K_(2)CO_(3) in the carbonaceous catalyst on the CH_(4)-CO_(2) reforming has been investigated with a fixed-bed reactor.It has been found that the carbonaceous catalyst is an efficient catalyst on CO_(2)-CH_(4) reforming.With the decrease of oxygen-bearing functional group,the catalytic activity of carbonaceous catalyst decreases quickly.The oxygen-bearing functional groups play a significant role in the carbonaceous-catalyzed CO_(2)-CH_(4) reforming;the ash components in carbonaceous catalyst also have an important influence on the CO_(2)-CH_(4) reforming.Fe_(2)O_(3),Na_(2)CO_(3),and K_(2)CO_(3) in the ash can catalyze the CO_(2)-CH_(4) reforming reaction;CaO has little effect on CO_(2)-CH_(4) reforming reaction.CaO can catalyze the gasification between carbonaceous catalyst and CO_(2);Al_(2)O_(3) and MgO inhibit the CO_(2)-CH_(4) reforming.展开更多
As a vital energy resource and raw material for many industrial products,syngas(CO and H_(2))is of great significance.Dry reforming of methane(DRM)is an important approach to producing syngas(with a hydrogen-to-carbon...As a vital energy resource and raw material for many industrial products,syngas(CO and H_(2))is of great significance.Dry reforming of methane(DRM)is an important approach to producing syngas(with a hydrogen-to-carbon-monoxide ratio of 1:1 in principle)from methane and carbon dioxide,with a lower operational cost as compared to other reforming techniques.However,many pure metallic catalysts used in DRM face deactivation issues due to coke formation or sintering of the metal particles.A systematic search for highly efficient metallic catalysts,which reduce the reaction barriers for the rate-determining steps and resist carbon deposition,is urgently needed.Nickel is a typical low-cost transition metal for activating the C–H bond in methane.In this work,we applied a two-step workflow to search for nickel-based bimetallic catalysts with doping metals M(M-Ni)by combining density functional theory(DFT)calculations and machine learning(ML).We focus on the two critical steps in DRM—CH_(4) and CO_(2) direct activations.We used DFT and slab models for the Ni(111)facet to explore the relevant reaction pathways and constructed a data set containing structural and energetic information for representative M-Ni systems.We used this dataset to train ML models with chemical-knowledge-based features and predicted CH_(4) and CO_(2) dissociation energies and barriers,which revealed the composition–activity relationships of the bimetallic catalysts.We also used these models to rank the predicted catalytic performance of candidate systems to demonstrate the applicability of ML for catalyst screening.We emphasized that ML ranking models would be more valuable than regression models in high-throughput screenings.Finally,we used our trained model to screen 12 unexplored M-Ni systems and showed that the DFT-computed energies and barriers are very close to the ML-predicted values for top candidates,validating the robustness of the trained model.展开更多
A co-precipitation method was employed to prepare Ni/Al_(2)O_(3)-ZrO_(2),Co/Al_(2)O_(3)-ZrO_(2)and Ni-Co/Al_(2)O_(3)-ZrO_(2)catalysts.Their properties were characterized by N_(2) adsorption(BET),thermogravimetric anal...A co-precipitation method was employed to prepare Ni/Al_(2)O_(3)-ZrO_(2),Co/Al_(2)O_(3)-ZrO_(2)and Ni-Co/Al_(2)O_(3)-ZrO_(2)catalysts.Their properties were characterized by N_(2) adsorption(BET),thermogravimetric analysis(TGA),temperature-programmed reduction(TPR),temperature-programmed desorption(CO_(2)-TPD),and temperature-programmed surface reaction(CH_(4)-TPSR and CO_(2)-TPSR).Ni-Co/Al_(2)O_(3)-ZrO_(2)bimetallic catalyst has good performance in the reduction of active components Ni,Co and CO_(2)adsorption.Compared with mono-metallic catalyst,bimetallic catalyst could provide more active sites and CO_(2)adsorption sites(C+CO_(2)=2CO)for the methane-reforming reaction,and a more appropriate force formed between active components and composite support(SMSI)for the catalytic reaction.According to the CH_(4)-CO_(2)-TPSR,there were 80.9%and 81.5%higher CH_(4) and CO_(2)conversion over Ni-Co/Al_(2)O_(3)-ZrO_(2)catalyst,and its better resistance to carbon deposition,less than 0.5%of coke after 4 h reaction,was found by TGA.The high activity and excellent anti-coking of the Ni-Co/Al_(2)O_(3)-ZrO_(2)catalyst were closely related to the synergy between Ni and Co active metal,the strong metal-support interaction and the use of composite support.展开更多
文摘The cobalt precursor affects the catalytic performance of Co/SiO_2 catalyst remarkably. The catalyst prepared from cobalt acetate exhibits excellent activity, stability and resistance to carbon deposition.
基金the National Basic Research Program of China(Grant No.2005CB221202)Shanxi Provincial Natural Science Foundation(20051020)for financial support of the present study。
文摘An investigation was made using a continuous fixed bed reactor to understand the influence of carbon deposition obtained under different conditions on CH_(4)-CO_(2)reforming.Thermogravimetry(TG)and X-ray diffraction(XRD)were employed to study the characteristics of carbon deposition.It was found that the carbonaceous catalyst is an efficient catalyst in methane decomposition and CH_(4)-CO_(2)reforming.The trend of methane decomposition at lower temperatures is similar to that at higher temperatures.The methane conversion is high during the initial of stage of the reaction,and then decays to a relatively fixed value after about 30 min.With temperature increase,the methane decomposition rate increases quickly.The reaction temperature has significant influence on methane decomposition,whereas the carbon deposition does not affect methane decomposition significantly.Different types of carbon deposition were formed at different methane decomposition reaction temperatures.The carbon deposition Type I generated at 900℃ has a minor effect on CH_(4)-CO_(2)reforming and it easily reacts with carbon dioxide,but the carbon deposition Type II generated at 1000℃and 1100℃clearly inhibits CH_(4)-CO_(2)reforming and it is difficult to react with carbon dioxide.The results of XRD showed that some graphite structures were found in carbon deposition Type II.
基金the National Basic Research Program of China(2005CB221202)Shanxi Provincial Natural Science Foundation(20051020)for financial support of the present study。
文摘A kind of new catalyst-carbonaceous catalyst-for CH_(4)-CO_(2) reformation has been developed in our laboratory.The effect of both oxygen-bearing functional group such as phenolic hydroxyl,carbonyl,carboxyl,and lactonic,and ash such as Fe_(2)O_(3),Na_(2)CO_(3),and K_(2)CO_(3) in the carbonaceous catalyst on the CH_(4)-CO_(2) reforming has been investigated with a fixed-bed reactor.It has been found that the carbonaceous catalyst is an efficient catalyst on CO_(2)-CH_(4) reforming.With the decrease of oxygen-bearing functional group,the catalytic activity of carbonaceous catalyst decreases quickly.The oxygen-bearing functional groups play a significant role in the carbonaceous-catalyzed CO_(2)-CH_(4) reforming;the ash components in carbonaceous catalyst also have an important influence on the CO_(2)-CH_(4) reforming.Fe_(2)O_(3),Na_(2)CO_(3),and K_(2)CO_(3) in the ash can catalyze the CO_(2)-CH_(4) reforming reaction;CaO has little effect on CO_(2)-CH_(4) reforming reaction.CaO can catalyze the gasification between carbonaceous catalyst and CO_(2);Al_(2)O_(3) and MgO inhibit the CO_(2)-CH_(4) reforming.
基金support provided by the American Chemical Society Petroleum Research Fund(PRF No.65744-DNI6).
文摘As a vital energy resource and raw material for many industrial products,syngas(CO and H_(2))is of great significance.Dry reforming of methane(DRM)is an important approach to producing syngas(with a hydrogen-to-carbon-monoxide ratio of 1:1 in principle)from methane and carbon dioxide,with a lower operational cost as compared to other reforming techniques.However,many pure metallic catalysts used in DRM face deactivation issues due to coke formation or sintering of the metal particles.A systematic search for highly efficient metallic catalysts,which reduce the reaction barriers for the rate-determining steps and resist carbon deposition,is urgently needed.Nickel is a typical low-cost transition metal for activating the C–H bond in methane.In this work,we applied a two-step workflow to search for nickel-based bimetallic catalysts with doping metals M(M-Ni)by combining density functional theory(DFT)calculations and machine learning(ML).We focus on the two critical steps in DRM—CH_(4) and CO_(2) direct activations.We used DFT and slab models for the Ni(111)facet to explore the relevant reaction pathways and constructed a data set containing structural and energetic information for representative M-Ni systems.We used this dataset to train ML models with chemical-knowledge-based features and predicted CH_(4) and CO_(2) dissociation energies and barriers,which revealed the composition–activity relationships of the bimetallic catalysts.We also used these models to rank the predicted catalytic performance of candidate systems to demonstrate the applicability of ML for catalyst screening.We emphasized that ML ranking models would be more valuable than regression models in high-throughput screenings.Finally,we used our trained model to screen 12 unexplored M-Ni systems and showed that the DFT-computed energies and barriers are very close to the ML-predicted values for top candidates,validating the robustness of the trained model.
基金supported by the National Basic Research Program of China(2005CB221207)the National Natural Science Foundation of China(Grants Nos.20846002,U0970134)+2 种基金the Program for Changjiang Scholars and Innovative Research Team in University(No.IRT0517)the Program for New Century Excellent Talents in University(No.NCET-05-0267)the Ph.D.Programs Foundation for New Teacher(No.20091402120013)in Ministry of Education,China。
文摘A co-precipitation method was employed to prepare Ni/Al_(2)O_(3)-ZrO_(2),Co/Al_(2)O_(3)-ZrO_(2)and Ni-Co/Al_(2)O_(3)-ZrO_(2)catalysts.Their properties were characterized by N_(2) adsorption(BET),thermogravimetric analysis(TGA),temperature-programmed reduction(TPR),temperature-programmed desorption(CO_(2)-TPD),and temperature-programmed surface reaction(CH_(4)-TPSR and CO_(2)-TPSR).Ni-Co/Al_(2)O_(3)-ZrO_(2)bimetallic catalyst has good performance in the reduction of active components Ni,Co and CO_(2)adsorption.Compared with mono-metallic catalyst,bimetallic catalyst could provide more active sites and CO_(2)adsorption sites(C+CO_(2)=2CO)for the methane-reforming reaction,and a more appropriate force formed between active components and composite support(SMSI)for the catalytic reaction.According to the CH_(4)-CO_(2)-TPSR,there were 80.9%and 81.5%higher CH_(4) and CO_(2)conversion over Ni-Co/Al_(2)O_(3)-ZrO_(2)catalyst,and its better resistance to carbon deposition,less than 0.5%of coke after 4 h reaction,was found by TGA.The high activity and excellent anti-coking of the Ni-Co/Al_(2)O_(3)-ZrO_(2)catalyst were closely related to the synergy between Ni and Co active metal,the strong metal-support interaction and the use of composite support.
