This study investigates the dry reformation of methane(DRM)over Ni/Al_(2)O_(3)catalysts in a dielectric barrier discharge(DBD)non-thermal plasma reactor.A novel hybrid machine learning(ML)model is developed to optimiz...This study investigates the dry reformation of methane(DRM)over Ni/Al_(2)O_(3)catalysts in a dielectric barrier discharge(DBD)non-thermal plasma reactor.A novel hybrid machine learning(ML)model is developed to optimize the plasma-catalytic DRM reaction with limited experimental data.To address the non-linear and complex nature of the plasma-catalytic DRM process,the hybrid ML model integrates three well-established algorithms:regression trees,support vector regression,and artificial neural networks.A genetic algorithm(GA)is then used to optimize the hyperparameters of each algorithm within the hybrid ML model.The ML model achieved excellent agreement with the experimental data,demonstrating its efficacy in accurately predicting and optimizing the DRM process.The model was subsequently used to investigate the impact of various operating parameters on the plasma-catalytic DRM performance.We found that the optimal discharge power(20 W),CO_(2)/CH_(4)molar ratio(1.5),and Ni loading(7.8 wt%)resulted in the maximum energy yield at a total flow rate of∼51 mL/min.Furthermore,we investigated the relative significance of each operating parameter on the performance of the plasma-catalytic DRM process.The results show that the total flow rate had the greatest influence on the conversion,with a significance exceeding 35%for each output,while the Ni loading had the least impact on the overall reaction performance.This hybrid model demonstrates a remarkable ability to extract valuable insights from limited datasets,enabling the development and optimization of more efficient and selective plasma-catalytic chemical processes.展开更多
The electroreduction reaction of CO_(2)(ECO_(2)RR)requires high-performance catalysts to convert CO_(2)into useful chemicals.Transition metal-based atomically dispersed catalysts are promising for the high selectivity...The electroreduction reaction of CO_(2)(ECO_(2)RR)requires high-performance catalysts to convert CO_(2)into useful chemicals.Transition metal-based atomically dispersed catalysts are promising for the high selectivity and activity in ECO_(2)RR.This work presents a series of atomically dispersed Co,Fe bimetallic catalysts by carbonizing the Fe-introduced Co-zeolitic-imidazolate-framework(C-Fe-Co-ZIF)for the syngas generation from ECO_(2)RR.The synergistic effect of the bimetallic catalyst promotes CO production.Compared to the pure C-Co-ZiF,C-Fe-Co-ZIF facilitates CO production with a CO Faradaic efficiency(FE)boost of 10%,with optimal FE_(CO)of 51.9%,FE_(H_(2))of 42.4%at-0.55 V,and CO current density of 8.0 mA cm^(-2)at-0.7 V versus reversible hydrogen electrode(RHE).The H_(2)/CO ratio is tunable from 0.8 to 4.2 in a wide potential window of-0.35 to-0.8 V versus RHE.The total FE_(CO+H_(2))maintains as high as 93%over 10 h.The proper adding amount of Fe could increase the number of active sites and create mild distortions for the nanoscopic environments of Co and Fe,which is essential for the enhancement of the CO production in ECO_(2)RR.The positive impacts of Cu-Co and Ni-Co bimetallic catalysts demonstrate the versatility and potential application of the bimetallic strategy for ECO_(2)RR.展开更多
A kind of solar thermochemical cycle based on methanothermal reduction of SnO2 is proposed for H2 and CO production. We find that the oxygen release capacity and thermodynamic driven force for methanothermal reduction...A kind of solar thermochemical cycle based on methanothermal reduction of SnO2 is proposed for H2 and CO production. We find that the oxygen release capacity and thermodynamic driven force for methanothermal reduction of SnO2 are large, and suggest CH4 :SnO2 = 2:1 as the feasible reduction condition for achieving high purities of syngas and avoiding vaporization of produced Sn. Subsequently, the amount of H2 and energetic upgrade factors under different oxidation conditions are compared, in which excess water vapor is found beneficial for hydrogen production and fuel energetic upgradation. Moreover, the effect of incom plete recovery of SnO2 on the subsequent cycle is underscored and explained. After accounting for factors such as isothermal operation and cycle stability, CH4 :SnO2 = 2:1 and H2O:Sn = 4:1 are suggested for highest solar-to-fuel efficiency of 46.1% at nonisothermal condition, where the reduction and oxidation temperature are 1400 and 600 K, respectively.展开更多
In this work, experimental studies of biomass gasification under different operating conditions were carried out in an updraft gasifier combined with a copper slag reformer. The influence of gasification temperature, ...In this work, experimental studies of biomass gasification under different operating conditions were carried out in an updraft gasifier combined with a copper slag reformer. The influence of gasification temperature, equivalence ratio （ER） and copper slag catalyst addition on gas production and tar yield were investigated. The experimental results showed that the content of H2 and CO, gas yield and LHV increased, while the tar yield and the content of CO2, CH4 and C2Hx in the gas product decreased with the temperature. At 800℃, with the increase of ER, the LHV, the tar yield and the content of H2, CO, CH4 and C2H2 in gas products decreased, while the gas yield and the content of CO2 increased. Copper slag was introduced into the secondary reformer for tar decomposition. The Fe3O4 phase in the fresh copper slag was reduced to FeO （Fe^2＋） and metallic Fe by the gas product. Fe species （FeO and metallic Fe） acted as the active sites for tar catalytic decomposition. The catalytic temperature had a significant influence on tar conversion and the composition of the gas product. Typically, the tar conversion of about 17%-54% could be achieved when the catalytic temperature was varied from 750 to 950 ℃. Also, the content of H2 and CO increased with the catalytic temperature, while that of CO2, CH4 and C2Hx in the gas product decreased. It was demonstrated that copper slag was a good catalyst for upgrading the gas product from biomass gasification.展开更多
The chemical looping reforming of methane through the nonstoichiometric ceria redox cycle(CeO2/CeO2-δ) has been experimentally investigated in a directly irradiated solar reactor to convert both solar energy and meth...The chemical looping reforming of methane through the nonstoichiometric ceria redox cycle(CeO2/CeO2-δ) has been experimentally investigated in a directly irradiated solar reactor to convert both solar energy and methane to syngas in the temperature range 900–1050 °C. Experiments were carried out with different ceria shapes via two-step redox cycling composed of endothermic partial reduction of ceria with methane and complete exothermic re-oxidation of reduced ceria with H2 O/CO2 at the same operating temperature, thereby demonstrating the capability to operate the cycle isothermally. A parametric study considering different ceria macrostructure variants(ceria packed powder, ceria packed powder mixed with inert Al2 O3 particles, and ceria reticulated porous foam) and operating parameters(methane flow-rate, reduction temperature, or sintering temperature) was conducted in order to unravel their impact on the bed-averaged oxygen non-stoichiometry(δ), syngas yield, methane conversion, and solar reactor performance. The ceria cycling stability was also experimentally investigated to demonstrate repeatable syngas production by alternating the flow between CH4 and H2 O(or CO2). A decrease in sintering temperature of the ceria foam was beneficial for increasing syngas selectivity, methane conversion,and reactor performance. Increasing both CH4 concentration and reduction temperature enhanced δ with the maximum value up to 0.41 but concomitantly favored CH4 cracking reaction. The ceria reticulated porous foam showed better performance in terms of effective heat transfer, due to volumetric absorption of concentrated solar radiation and uniform heating with lower solar power consumption, thereby promoting the solar-to-fuel energy conversion efficiency that reached up to 5.60%. The energy upgrade factor achieved during cycle was up to 1.19. Stable patterns in the δ and syngas yield for consecutive cycles with the ceria foam validated material performance stability.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
This paper presents a comparatively experimental study of nitrogen oxide (NOx) emissions from an internal combustion engine fed by gasoline available in the Saudi Arabian market rating octane number (RON 91 and RON 95...This paper presents a comparatively experimental study of nitrogen oxide (NOx) emissions from an internal combustion engine fed by gasoline available in the Saudi Arabian market rating octane number (RON 91 and RON 95) with admixtures of syngas with 0% E0, 5% E5 and 10% E10—by volume of pure ethanol—and HE5 and HE10 with water concentrations of 5%, 10%, 30% and 40%—by volume of hydrous ethanol—at stoichio-metric mixtures. An on-board plasma system used to produce syngas through the partial oxidation of gasoline with air in a plasma-assisted fuel reformer. The syngas injected in a gasoline engine with a fuel injection system modified for operation with addition of some amount of syngas. The experimental results demonstrated a significant total reduction in NOx emissions and slightly increased in fuel consumption when mixing gasoline (RON 91 and RON 95), ethanol (E5 and E10) and hydrous ethanol (HE5 and HE10) with syngas. For the use of hydrous ethanol (HE5 and HE10) along with the addition of syngas, for both RON 91 and RON 95, the lowest NOx emissions are found 72% with a water concentration of 40%.展开更多
The behavior of metallic structured perovskite-based catalysts was evaluated in the combined methane reforming reaction with CO2-O2. The reaction conditions were established by varying the reaction temperature and rea...The behavior of metallic structured perovskite-based catalysts was evaluated in the combined methane reforming reaction with CO2-O2. The reaction conditions were established by varying the reaction temperature and reactor input composition in the range of 650 to 850℃ and CH4/CO2 ratio 1 to 5, respectively. The results of the catalytic tests at 750℃ showed a positive effect of the metallic structure, producing higher conversions and H2/CO ratios in the products compare to that obtained with the powder catalyst.展开更多
基金This project received funding from the European Union’s Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreement No. 813393the funding from the National Natural Science Foundation of China (No. 52177149)
文摘This study investigates the dry reformation of methane(DRM)over Ni/Al_(2)O_(3)catalysts in a dielectric barrier discharge(DBD)non-thermal plasma reactor.A novel hybrid machine learning(ML)model is developed to optimize the plasma-catalytic DRM reaction with limited experimental data.To address the non-linear and complex nature of the plasma-catalytic DRM process,the hybrid ML model integrates three well-established algorithms:regression trees,support vector regression,and artificial neural networks.A genetic algorithm(GA)is then used to optimize the hyperparameters of each algorithm within the hybrid ML model.The ML model achieved excellent agreement with the experimental data,demonstrating its efficacy in accurately predicting and optimizing the DRM process.The model was subsequently used to investigate the impact of various operating parameters on the plasma-catalytic DRM performance.We found that the optimal discharge power(20 W),CO_(2)/CH_(4)molar ratio(1.5),and Ni loading(7.8 wt%)resulted in the maximum energy yield at a total flow rate of∼51 mL/min.Furthermore,we investigated the relative significance of each operating parameter on the performance of the plasma-catalytic DRM process.The results show that the total flow rate had the greatest influence on the conversion,with a significance exceeding 35%for each output,while the Ni loading had the least impact on the overall reaction performance.This hybrid model demonstrates a remarkable ability to extract valuable insights from limited datasets,enabling the development and optimization of more efficient and selective plasma-catalytic chemical processes.
基金This work is supported financially by the Natural Sciences and Engineering Research Council of Canada(NSERC),the Fonds de Recherche du Québec-Nature et Technologies(FRQNT)Centre Québécois sur les Materiaux Fonctionnels(CQMF),the Canada Foundation for Innovation(CFI)+1 种基金Institut National de la Recherche Scientifique(INRS).The XAS characterizations were performed at the Canadian Light Source(CLS),which is financially supported by NSERC,CFIthe University of Saskatchewan,the Government of Saskatchewan,Western Economic Diversification Canada,the National Research Council of Canada,and the Canadian Institutes of Health Research。
文摘The electroreduction reaction of CO_(2)(ECO_(2)RR)requires high-performance catalysts to convert CO_(2)into useful chemicals.Transition metal-based atomically dispersed catalysts are promising for the high selectivity and activity in ECO_(2)RR.This work presents a series of atomically dispersed Co,Fe bimetallic catalysts by carbonizing the Fe-introduced Co-zeolitic-imidazolate-framework(C-Fe-Co-ZIF)for the syngas generation from ECO_(2)RR.The synergistic effect of the bimetallic catalyst promotes CO production.Compared to the pure C-Co-ZiF,C-Fe-Co-ZIF facilitates CO production with a CO Faradaic efficiency(FE)boost of 10%,with optimal FE_(CO)of 51.9%,FE_(H_(2))of 42.4%at-0.55 V,and CO current density of 8.0 mA cm^(-2)at-0.7 V versus reversible hydrogen electrode(RHE).The H_(2)/CO ratio is tunable from 0.8 to 4.2 in a wide potential window of-0.35 to-0.8 V versus RHE.The total FE_(CO+H_(2))maintains as high as 93%over 10 h.The proper adding amount of Fe could increase the number of active sites and create mild distortions for the nanoscopic environments of Co and Fe,which is essential for the enhancement of the CO production in ECO_(2)RR.The positive impacts of Cu-Co and Ni-Co bimetallic catalysts demonstrate the versatility and potential application of the bimetallic strategy for ECO_(2)RR.
基金supported by the National Key R&D Program of China (Grant no. 2018YFB1502005)the National Natural Science Foundation of China (Grant nos. 51476163 , 51806209 and 81801768)Institute of Electrical Engineering, Chinese Academy of Sciences (No.Y770111CSC)
文摘A kind of solar thermochemical cycle based on methanothermal reduction of SnO2 is proposed for H2 and CO production. We find that the oxygen release capacity and thermodynamic driven force for methanothermal reduction of SnO2 are large, and suggest CH4 :SnO2 = 2:1 as the feasible reduction condition for achieving high purities of syngas and avoiding vaporization of produced Sn. Subsequently, the amount of H2 and energetic upgrade factors under different oxidation conditions are compared, in which excess water vapor is found beneficial for hydrogen production and fuel energetic upgradation. Moreover, the effect of incom plete recovery of SnO2 on the subsequent cycle is underscored and explained. After accounting for factors such as isothermal operation and cycle stability, CH4 :SnO2 = 2:1 and H2O:Sn = 4:1 are suggested for highest solar-to-fuel efficiency of 46.1% at nonisothermal condition, where the reduction and oxidation temperature are 1400 and 600 K, respectively.
基金supported by the National Natural Science Foundation of China (No.50906035)the Applied Basic Research Foundation of Yunnan Province (No. 2009ZC014M)the Scientific Research Foundation of Educational Commission of Yunnan Province (No. 09Z0015)
文摘In this work, experimental studies of biomass gasification under different operating conditions were carried out in an updraft gasifier combined with a copper slag reformer. The influence of gasification temperature, equivalence ratio （ER） and copper slag catalyst addition on gas production and tar yield were investigated. The experimental results showed that the content of H2 and CO, gas yield and LHV increased, while the tar yield and the content of CO2, CH4 and C2Hx in the gas product decreased with the temperature. At 800℃, with the increase of ER, the LHV, the tar yield and the content of H2, CO, CH4 and C2H2 in gas products decreased, while the gas yield and the content of CO2 increased. Copper slag was introduced into the secondary reformer for tar decomposition. The Fe3O4 phase in the fresh copper slag was reduced to FeO （Fe^2＋） and metallic Fe by the gas product. Fe species （FeO and metallic Fe） acted as the active sites for tar catalytic decomposition. The catalytic temperature had a significant influence on tar conversion and the composition of the gas product. Typically, the tar conversion of about 17%-54% could be achieved when the catalytic temperature was varied from 750 to 950 ℃. Also, the content of H2 and CO increased with the catalytic temperature, while that of CO2, CH4 and C2Hx in the gas product decreased. It was demonstrated that copper slag was a good catalyst for upgrading the gas product from biomass gasification.
基金The King Mongkut’s Institute of Technology Ladkrabang(KMITL),Thailandthe Franco-Thai scholarship program。
文摘The chemical looping reforming of methane through the nonstoichiometric ceria redox cycle(CeO2/CeO2-δ) has been experimentally investigated in a directly irradiated solar reactor to convert both solar energy and methane to syngas in the temperature range 900–1050 °C. Experiments were carried out with different ceria shapes via two-step redox cycling composed of endothermic partial reduction of ceria with methane and complete exothermic re-oxidation of reduced ceria with H2 O/CO2 at the same operating temperature, thereby demonstrating the capability to operate the cycle isothermally. A parametric study considering different ceria macrostructure variants(ceria packed powder, ceria packed powder mixed with inert Al2 O3 particles, and ceria reticulated porous foam) and operating parameters(methane flow-rate, reduction temperature, or sintering temperature) was conducted in order to unravel their impact on the bed-averaged oxygen non-stoichiometry(δ), syngas yield, methane conversion, and solar reactor performance. The ceria cycling stability was also experimentally investigated to demonstrate repeatable syngas production by alternating the flow between CH4 and H2 O(or CO2). A decrease in sintering temperature of the ceria foam was beneficial for increasing syngas selectivity, methane conversion,and reactor performance. Increasing both CH4 concentration and reduction temperature enhanced δ with the maximum value up to 0.41 but concomitantly favored CH4 cracking reaction. The ceria reticulated porous foam showed better performance in terms of effective heat transfer, due to volumetric absorption of concentrated solar radiation and uniform heating with lower solar power consumption, thereby promoting the solar-to-fuel energy conversion efficiency that reached up to 5.60%. The energy upgrade factor achieved during cycle was up to 1.19. Stable patterns in the δ and syngas yield for consecutive cycles with the ceria foam validated material performance stability.
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.
文摘This paper presents a comparatively experimental study of nitrogen oxide (NOx) emissions from an internal combustion engine fed by gasoline available in the Saudi Arabian market rating octane number (RON 91 and RON 95) with admixtures of syngas with 0% E0, 5% E5 and 10% E10—by volume of pure ethanol—and HE5 and HE10 with water concentrations of 5%, 10%, 30% and 40%—by volume of hydrous ethanol—at stoichio-metric mixtures. An on-board plasma system used to produce syngas through the partial oxidation of gasoline with air in a plasma-assisted fuel reformer. The syngas injected in a gasoline engine with a fuel injection system modified for operation with addition of some amount of syngas. The experimental results demonstrated a significant total reduction in NOx emissions and slightly increased in fuel consumption when mixing gasoline (RON 91 and RON 95), ethanol (E5 and E10) and hydrous ethanol (HE5 and HE10) with syngas. For the use of hydrous ethanol (HE5 and HE10) along with the addition of syngas, for both RON 91 and RON 95, the lowest NOx emissions are found 72% with a water concentration of 40%.
文摘The behavior of metallic structured perovskite-based catalysts was evaluated in the combined methane reforming reaction with CO2-O2. The reaction conditions were established by varying the reaction temperature and reactor input composition in the range of 650 to 850℃ and CH4/CO2 ratio 1 to 5, respectively. The results of the catalytic tests at 750℃ showed a positive effect of the metallic structure, producing higher conversions and H2/CO ratios in the products compare to that obtained with the powder catalyst.
