The Fischer–Tropsch to olefins(FTO) process is a method for the direct conversion of synthesis gas to lower C–Colefins. Carbon-supported iron carbide nanoparticles are attractive catalysts for this reaction.The ca...The Fischer–Tropsch to olefins(FTO) process is a method for the direct conversion of synthesis gas to lower C–Colefins. Carbon-supported iron carbide nanoparticles are attractive catalysts for this reaction.The catalytic activity can be improved and undesired formation of alkanes can be suppressed by the addition of sodium and sulfur as promoters but the influence of their content and ratio remains poorly understood and the promoted catalysts often suffer from rapid deactivation due to particle growth. A series of carbon black-supported iron catalysts with similar iron content and nominal sodium/sulfur loadings of 1–30/0.5–5 wt% with respect to iron are prepared and characterized under FTO conditions at 1and 10 bar syngas pressure to illuminate the influence of the promoter level on the catalytic properties.Iron particles and promoters undergo significant reorganization during FTO operation under industrially relevant conditions. Low sodium content(1–3 wt%) leads to a delay in iron carbide formation. Sodium contents of 15–30 wt% lead to rapid loss of catalytic activity due to the covering of the iron surface with promoters during particle growth under FTO operation. Higher activity and slower loss of activity are observed at low promoter contents(1–3 wt% sodium and 0.5–1 wt% sulfur) but a minimum amount of alkali is required to effectively suppress methane and C–Cparaffin formation. A reference catalyst support(carbide-derived carbon aerogel) shows that the optimum promoter level depends on iron particle size and support pore structure.展开更多
The deactivation behavior by crystallite growth of nickel nanoparticles on various supports(carbon nanofibers, zirconia, Si C, α-Al2O3 and γ-Al2O3) was investigated in the aqueous phase reforming of ethylene glyco...The deactivation behavior by crystallite growth of nickel nanoparticles on various supports(carbon nanofibers, zirconia, Si C, α-Al2O3 and γ-Al2O3) was investigated in the aqueous phase reforming of ethylene glycol. Supported Ni catalysts of ~10 wt% were prepared by impregnation of carbon nanofibers(CNF),Zr O2, SiC, γ-Al2O3 and α-Al2O3. The extent of the Ni nanoparticle growth on various support materials follows the order CNF ~ ZrO2〉 SiC 〉 γ-Al2O3〉〉 α-Al2O3 which sequence, however, was determined by the initial Ni particle size. Based on the observed nickel leaching and the specific growth characteristics; the particle size distribution and the effect of loading on the growth rate, Ostwald ripening is suggested to be the main mechanism contributing to nickel particle growth. Remarkably, initially smaller Ni particles(~12 nm) supported on α-Al2O3 were found to outgrow Ni particles with initially larger size(~20 nm). It is put forward that the higher susceptibility with respect to oxidation of the smaller Ni nanoparticles and differences in initial particle size distribution are responsible for this behavior.展开更多
The article Assessment of oxide nanoparticle stability in liquid phase transmission electron microscopy written by Mark J.Meijerink,Krijn P.de Jong,and Jovana Zecevic,was originally published electronically on the pub...The article Assessment of oxide nanoparticle stability in liquid phase transmission electron microscopy written by Mark J.Meijerink,Krijn P.de Jong,and Jovana Zecevic,was originally published electronically on the publisher's internet portal(currently SpringerLink)on 22 May 2019 without open access.The copyright of the article changed on 3 June 2019 to c The Author(s)2019 and the article is forthwith distributed under the terms of the Creative Commons Attribution 4.0 International License(http://creativecommons.Org/licenses/by/4.0/),which permits use,duplication,adaptation,distribution and reproduction in any medium or format,as long as you give appropriate credit to the original author(s)and the source,provide a link to the Creative Commons license and indicate if changes were made.展开更多
基金supported by a Post Doc grant of the German Academic Exchange Service(Deutscher Akademischer Austauschdienst,DAAD grant no.91552012)by the European Research Council(EU FP7 ERC advanced grant no.338846)
文摘The Fischer–Tropsch to olefins(FTO) process is a method for the direct conversion of synthesis gas to lower C–Colefins. Carbon-supported iron carbide nanoparticles are attractive catalysts for this reaction.The catalytic activity can be improved and undesired formation of alkanes can be suppressed by the addition of sodium and sulfur as promoters but the influence of their content and ratio remains poorly understood and the promoted catalysts often suffer from rapid deactivation due to particle growth. A series of carbon black-supported iron catalysts with similar iron content and nominal sodium/sulfur loadings of 1–30/0.5–5 wt% with respect to iron are prepared and characterized under FTO conditions at 1and 10 bar syngas pressure to illuminate the influence of the promoter level on the catalytic properties.Iron particles and promoters undergo significant reorganization during FTO operation under industrially relevant conditions. Low sodium content(1–3 wt%) leads to a delay in iron carbide formation. Sodium contents of 15–30 wt% lead to rapid loss of catalytic activity due to the covering of the iron surface with promoters during particle growth under FTO operation. Higher activity and slower loss of activity are observed at low promoter contents(1–3 wt% sodium and 0.5–1 wt% sulfur) but a minimum amount of alkali is required to effectively suppress methane and C–Cparaffin formation. A reference catalyst support(carbide-derived carbon aerogel) shows that the optimum promoter level depends on iron particle size and support pore structure.
基金the support of the Smart Mix Program of The Netherlands Ministry of Economic Affairs, Agriculture and Innovation and The Netherlands Ministry of Education, Culture and Science (Grant no. 053.70.011)
文摘The deactivation behavior by crystallite growth of nickel nanoparticles on various supports(carbon nanofibers, zirconia, Si C, α-Al2O3 and γ-Al2O3) was investigated in the aqueous phase reforming of ethylene glycol. Supported Ni catalysts of ~10 wt% were prepared by impregnation of carbon nanofibers(CNF),Zr O2, SiC, γ-Al2O3 and α-Al2O3. The extent of the Ni nanoparticle growth on various support materials follows the order CNF ~ ZrO2〉 SiC 〉 γ-Al2O3〉〉 α-Al2O3 which sequence, however, was determined by the initial Ni particle size. Based on the observed nickel leaching and the specific growth characteristics; the particle size distribution and the effect of loading on the growth rate, Ostwald ripening is suggested to be the main mechanism contributing to nickel particle growth. Remarkably, initially smaller Ni particles(~12 nm) supported on α-Al2O3 were found to outgrow Ni particles with initially larger size(~20 nm). It is put forward that the higher susceptibility with respect to oxidation of the smaller Ni nanoparticles and differences in initial particle size distribution are responsible for this behavior.
文摘The article Assessment of oxide nanoparticle stability in liquid phase transmission electron microscopy written by Mark J.Meijerink,Krijn P.de Jong,and Jovana Zecevic,was originally published electronically on the publisher's internet portal(currently SpringerLink)on 22 May 2019 without open access.The copyright of the article changed on 3 June 2019 to c The Author(s)2019 and the article is forthwith distributed under the terms of the Creative Commons Attribution 4.0 International License(http://creativecommons.Org/licenses/by/4.0/),which permits use,duplication,adaptation,distribution and reproduction in any medium or format,as long as you give appropriate credit to the original author(s)and the source,provide a link to the Creative Commons license and indicate if changes were made.