Several ternary oxides CuCeZrO_(y)(CCZ)were synthesized by a facile grinding method followed by calcination at high temperatures,and used as catalysts for CO oxidation at low temperatures.The influences of calcination...Several ternary oxides CuCeZrO_(y)(CCZ)were synthesized by a facile grinding method followed by calcination at high temperatures,and used as catalysts for CO oxidation at low temperatures.The influences of calcination temperature(400-600℃)on the physicochemical properties of the assynthesized ternary oxides were investigated by thermogravimetric analysis/differential scanning calorimetry(TGA/DSC),X-ray diffraction(XRD),transmission electron microscopy(TEM),Raman,inductively coupled plasma-optical emission spectrometry(ICP-OES),N_(2) adsorption,H_(2)-temperature programmed reduction(H_(2)-TPR),and X-ray photoelectron spectroscopy(XPS)characterizations.The results show that the increase in calcination temperature from 400 to 500℃is conducive to the high dispersion of CuOx on catalyst surface and the incorporation of Cu species into the support to form the Cu-Ce-Zr-O solid solution.Further raising of calcination temperature from 500 to 600℃,however,leads to the segregation of Cu species from the solid solution to aggregate on support surface and growth of highly dispersed CuOx nanoparticles.The highest catalytic activity is acquired over the CCZ calcined at 500℃,which can be ascribed to the largest contents of Cu+species and oxygen vacancies owing to the formation of the maximum amount of Cu-Ce-Zr-O solid solution.展开更多
Methyl methoxyacetate(MMAc)and methyl formate(MF)can be produced directly by heterogeneous zeolite-catalyzed carbonylation and disproportionation of dimethoxymethane(DMM),with near 100%selectivity for each process.Des...Methyl methoxyacetate(MMAc)and methyl formate(MF)can be produced directly by heterogeneous zeolite-catalyzed carbonylation and disproportionation of dimethoxymethane(DMM),with near 100%selectivity for each process.Despite continuous research efforts,the insight into the reaction mechanism and kinetics theory are still in their nascent stage.In this study,ZEO-1 material,a zeolite with up to now the largest cages comprising 16×16-MRs,16×12-MRs,and 12×12-MRs,was explored for DMM carbonylation and disproportionation reactions.The rate of MMAc formation based on accessible Brönsted acid sites is 2.5 times higher for ZEO-1(Si/Al=21)relative to the previously investigated FAU(Si/Al=15),indicating the positive effect of spatial separation of active sites in ZEO-1 on catalytic activity.A higher MF formation rate is also observed over ZEO-1 with lower activation energy(79.94 vs.95.19 kJ/mol)compared with FAU(Si/Al=30).Two types of active sites are proposed within ZEO-1 zeolite:Site 1 located in large cages formed by 16×16-MRs and 16×12-MRs,which is active predominantly for MMAc formation,and Site 2 located in smaller cages for methyl formate/dimethyl ether formation.Kinetics investigation of DMM carbonylation over ZEO-1 exhibit a first-order dependence on CO partial pressure and a slightly inverse-order dependence on DMM partial pressure.The DMM disproportionation is nearly first-order dependence on DMM partial pressure,while it reveals a strongly inverse dependence with increasing CO partial pressure.Furthermore,ZEO-1 exhibits good catalytic stability,and almost no deactivation is observed during the more than 70 h test with high carbonylation selectivity of above 89%,due to the well-enhanced diffusion property demonstrated by intelligent-gravimetric analysis.展开更多
Zeolites are characterized by their microporous,crystalline structures with a four-connected framework with variable compositions,predominantly aluminosilicates.They are extensively utilized as adsorbents,catalysts,an...Zeolites are characterized by their microporous,crystalline structures with a four-connected framework with variable compositions,predominantly aluminosilicates.They are extensively utilized as adsorbents,catalysts,and ion exchangers across domestic and industrial sectors.With the ongoing energy transition from fossil fuels to renewable sources and the pursuit of environmentally sustainable development,zeolites are increasingly being explored beyond their traditional application fields.They are investigated for their adsorption and catalytic capabilities in the protection and restoration of air,water,and soil quality,as well as in the environmentally friendly“green”production of chemicals.This review article details these novel and potential applications of zeolites,emphasizing the unique properties that render them suitable for each specific use case and discussing how these properties can be fine-tuned through material selection or tailored synthesis methods.展开更多
The use of an organic structure-directing agent(OSDA)makes zeolite synthesis expensive and environmentally non-friendly.Seeded zeolite synthesis offers an environmentally benign alternative that avoids using an OSDA w...The use of an organic structure-directing agent(OSDA)makes zeolite synthesis expensive and environmentally non-friendly.Seeded zeolite synthesis offers an environmentally benign alternative that avoids using an OSDA while providing a high purity,crystallinity,and yield in the product.In this study,we report using embryonic zeolites(EZs)as efficient seeds to obtain industrially important zeolites such as ZSM-34 and SSZ-13 in an OSDA-free synthesis system.Our results showed that zeolites ZSM-34,SSZ-13 and LTL could be obtained depending on the Al/Si ratio in the synthesis system.The synthesis time was considerably shorter than other ZSM-34 and SSZ-13 syntheses methods reported in the literature,achieving more than 90%crystallinity.The physicochemical analysis showed that highly crystalline zeolites with characteristics similar to the OSDA synthesized counterparts were obtained.Furthermore,the EZs seeding approach is facile,low cost,and environmentally friendly,pro-vided the synthesis is OSDA-free.In addition,the EZs seeds can be obtained under hydrothermal synthesis conditions.The method can be potentially applied to the synthesis of other zeolite types.展开更多
Zeolites are typically synthesized in alkaline or fluoride-containing near-neutral media.Sophisticated organic structure-directing agents have been investigated for such systems with the aim of discovering materials w...Zeolites are typically synthesized in alkaline or fluoride-containing near-neutral media.Sophisticated organic structure-directing agents have been investigated for such systems with the aim of discovering materials with unprecedented structures and properties for novel technical applications.In contrast,zeolite crystallization in strongly acidic media has yet to be explored.This study demonstrates that a zeolitic silicate phase crystallizes from acidic gels using trimethylamine as an organic additive with the composition 1 SiO_(2):0.3 TMA:0.3 HCl:0.15 HF:55 H_(2)O:(0.1-0.4)GeO_(2).This phase has an interrupted four-connected framework analog to the octahedron/tetrahedron-mixed framework of the mineral family pharmacosiderite.In comparison to the pharmacosiderite-type HK_(3)(Ge_(7)O_(16))(H_(2)O)_(4),the four GeO_(6)-octahedra forming the central[HGe_(4)O_(4)O_(12)]-cluster are replaced by four SiO_(4)-tetrahedra in a[Si_(4)O_(6)(OH)2.89]-unit in the new phase.However,the structure is distorted and may contain connectivity and point defects;thus,healing by the occasional incorporation of GeO_(6)-units is necessary.The refined unit cell has a cubic symmetry,space group P-43m(#215),with a=7.7005(1)Å.Acidic-medium synthesis is a useful way to find new zeolites that move in a fundamentally different direction from sophisticated organic structure-directing agents.展开更多
基金Project supported by the National Natural Science Foundation of China(21273150)。
文摘Several ternary oxides CuCeZrO_(y)(CCZ)were synthesized by a facile grinding method followed by calcination at high temperatures,and used as catalysts for CO oxidation at low temperatures.The influences of calcination temperature(400-600℃)on the physicochemical properties of the assynthesized ternary oxides were investigated by thermogravimetric analysis/differential scanning calorimetry(TGA/DSC),X-ray diffraction(XRD),transmission electron microscopy(TEM),Raman,inductively coupled plasma-optical emission spectrometry(ICP-OES),N_(2) adsorption,H_(2)-temperature programmed reduction(H_(2)-TPR),and X-ray photoelectron spectroscopy(XPS)characterizations.The results show that the increase in calcination temperature from 400 to 500℃is conducive to the high dispersion of CuOx on catalyst surface and the incorporation of Cu species into the support to form the Cu-Ce-Zr-O solid solution.Further raising of calcination temperature from 500 to 600℃,however,leads to the segregation of Cu species from the solid solution to aggregate on support surface and growth of highly dispersed CuOx nanoparticles.The highest catalytic activity is acquired over the CCZ calcined at 500℃,which can be ascribed to the largest contents of Cu+species and oxygen vacancies owing to the formation of the maximum amount of Cu-Ce-Zr-O solid solution.
文摘Methyl methoxyacetate(MMAc)and methyl formate(MF)can be produced directly by heterogeneous zeolite-catalyzed carbonylation and disproportionation of dimethoxymethane(DMM),with near 100%selectivity for each process.Despite continuous research efforts,the insight into the reaction mechanism and kinetics theory are still in their nascent stage.In this study,ZEO-1 material,a zeolite with up to now the largest cages comprising 16×16-MRs,16×12-MRs,and 12×12-MRs,was explored for DMM carbonylation and disproportionation reactions.The rate of MMAc formation based on accessible Brönsted acid sites is 2.5 times higher for ZEO-1(Si/Al=21)relative to the previously investigated FAU(Si/Al=15),indicating the positive effect of spatial separation of active sites in ZEO-1 on catalytic activity.A higher MF formation rate is also observed over ZEO-1 with lower activation energy(79.94 vs.95.19 kJ/mol)compared with FAU(Si/Al=30).Two types of active sites are proposed within ZEO-1 zeolite:Site 1 located in large cages formed by 16×16-MRs and 16×12-MRs,which is active predominantly for MMAc formation,and Site 2 located in smaller cages for methyl formate/dimethyl ether formation.Kinetics investigation of DMM carbonylation over ZEO-1 exhibit a first-order dependence on CO partial pressure and a slightly inverse-order dependence on DMM partial pressure.The DMM disproportionation is nearly first-order dependence on DMM partial pressure,while it reveals a strongly inverse dependence with increasing CO partial pressure.Furthermore,ZEO-1 exhibits good catalytic stability,and almost no deactivation is observed during the more than 70 h test with high carbonylation selectivity of above 89%,due to the well-enhanced diffusion property demonstrated by intelligent-gravimetric analysis.
基金supported by Shandong Energy Institute(SEI S202107),Nature Science Foundation of Shandong Province(ZR2022MB053 and ZR2022QB216).
文摘Zeolites are characterized by their microporous,crystalline structures with a four-connected framework with variable compositions,predominantly aluminosilicates.They are extensively utilized as adsorbents,catalysts,and ion exchangers across domestic and industrial sectors.With the ongoing energy transition from fossil fuels to renewable sources and the pursuit of environmentally sustainable development,zeolites are increasingly being explored beyond their traditional application fields.They are investigated for their adsorption and catalytic capabilities in the protection and restoration of air,water,and soil quality,as well as in the environmentally friendly“green”production of chemicals.This review article details these novel and potential applications of zeolites,emphasizing the unique properties that render them suitable for each specific use case and discussing how these properties can be fine-tuned through material selection or tailored synthesis methods.
文摘The use of an organic structure-directing agent(OSDA)makes zeolite synthesis expensive and environmentally non-friendly.Seeded zeolite synthesis offers an environmentally benign alternative that avoids using an OSDA while providing a high purity,crystallinity,and yield in the product.In this study,we report using embryonic zeolites(EZs)as efficient seeds to obtain industrially important zeolites such as ZSM-34 and SSZ-13 in an OSDA-free synthesis system.Our results showed that zeolites ZSM-34,SSZ-13 and LTL could be obtained depending on the Al/Si ratio in the synthesis system.The synthesis time was considerably shorter than other ZSM-34 and SSZ-13 syntheses methods reported in the literature,achieving more than 90%crystallinity.The physicochemical analysis showed that highly crystalline zeolites with characteristics similar to the OSDA synthesized counterparts were obtained.Furthermore,the EZs seeding approach is facile,low cost,and environmentally friendly,pro-vided the synthesis is OSDA-free.In addition,the EZs seeds can be obtained under hydrothermal synthesis conditions.The method can be potentially applied to the synthesis of other zeolite types.
基金support provided by the Shandong Energy Institute(SEI S202107)Nature Science Foundation of Shandong Province(ZR2022MB053 and ZR2022QB216).
文摘Zeolites are typically synthesized in alkaline or fluoride-containing near-neutral media.Sophisticated organic structure-directing agents have been investigated for such systems with the aim of discovering materials with unprecedented structures and properties for novel technical applications.In contrast,zeolite crystallization in strongly acidic media has yet to be explored.This study demonstrates that a zeolitic silicate phase crystallizes from acidic gels using trimethylamine as an organic additive with the composition 1 SiO_(2):0.3 TMA:0.3 HCl:0.15 HF:55 H_(2)O:(0.1-0.4)GeO_(2).This phase has an interrupted four-connected framework analog to the octahedron/tetrahedron-mixed framework of the mineral family pharmacosiderite.In comparison to the pharmacosiderite-type HK_(3)(Ge_(7)O_(16))(H_(2)O)_(4),the four GeO_(6)-octahedra forming the central[HGe_(4)O_(4)O_(12)]-cluster are replaced by four SiO_(4)-tetrahedra in a[Si_(4)O_(6)(OH)2.89]-unit in the new phase.However,the structure is distorted and may contain connectivity and point defects;thus,healing by the occasional incorporation of GeO_(6)-units is necessary.The refined unit cell has a cubic symmetry,space group P-43m(#215),with a=7.7005(1)Å.Acidic-medium synthesis is a useful way to find new zeolites that move in a fundamentally different direction from sophisticated organic structure-directing agents.
