Supported nickel catalysts are promising candidates for dry reforming of methane, but agglomeration of Ni^(0) and coke deposition hinder the industrial applications. Herein, we report a novel interface-directed synthe...Supported nickel catalysts are promising candidates for dry reforming of methane, but agglomeration of Ni^(0) and coke deposition hinder the industrial applications. Herein, we report a novel interface-directed synthetic approach to construct distinct metal ensembles by carefully tuning the compositions of the carriers. A Zr-Mn-Zn ternary oxide-supported Ni catalyst, together with the respective binary oxide-supported analogues, was synthesized by adopting a sequential co-precipitation and wetness impregnation method. Combined characterization techniques identify distinct catalyst models, including (i) conventional NiO nanoparticles with different sizes on Zr-Mn and Zr-Zn, and (ii) epitaxially growing NiO ensembles of a few nanometers thickness at the periphery of ZnO_(x) particles. These catalysts exhibit divergent responses in the catalytic testing, with the ternary oxide system significantly outperforming the binary analogues. The strong electronic interactions between Mn-Ni increase Ni dispersion and the activity while the stability is strengthened upon Zn addition. Both high activity, high selectivity, and remarkable stability are attained upon co-adding Mn and Zn. The interfaces between Ni and Zr-Mn-Zn rather than the physical contacts of individual oxide-supported analogues through mechanical mixing are keys for the outstanding performance.展开更多
Selective hydrogenation of 1,3‐butadiene is an essential process in the upgrading of the crude C4 cut from the petroleum chemical sector.Catalyst design is crucial to achieve a virtually alkadiene‐free product while...Selective hydrogenation of 1,3‐butadiene is an essential process in the upgrading of the crude C4 cut from the petroleum chemical sector.Catalyst design is crucial to achieve a virtually alkadiene‐free product while avoiding over‐hydrogenating valuable olefins.In addition to the great industrial relevance,this demanding selectivity pattern renders 1,3‐butadiene hydrogenation a widely used model reaction to discriminate selective hydrogenation catalysts in academia.Nonetheless,critical reviews on the catalyst development are extremely lacking in literature.In this review,we aim to provide the reader an in‐depth overview of different catalyst families,particularly the precious metal‐based monometallic catalysts(Pd,Pt,and Au),developed in the last half century.The emphasis is placed on the development of new strategies to design high‐performance architectures,the establishment of structure‐performance relationships,and the reaction and deactivation mechanisms.Thrilling directions for future optimization of catalyst formulations and engineering aspect are also provided.展开更多
Acetylene coupling with ethylene dichloride,which uses both coal and oil resources,is attractive for sustainable PVC manufacturing.Herein,highly active and stable carbon nitride‐based catalysts were developed by a no...Acetylene coupling with ethylene dichloride,which uses both coal and oil resources,is attractive for sustainable PVC manufacturing.Herein,highly active and stable carbon nitride‐based catalysts were developed by a novel pre‐oxidation‐pyrolysis process,affording unprecedented dehydrochlorination activity with good durability.The best‐performing system was further modified with different precious metals(Au,Pt,and Ru)to promote the hydrochlorination chemistry between the in‐situ formed hydrogen chloride and acetylene co‐feed.The presence of metal centers intensifies the hydrochlorination activity but weakens the dehydrochlorination ability due to competitive adsorption between the two reactants at the metal sites.Superior coupling performance was achieved over C_(3)N_(4)/AC and single‐atom Au/C_(3)N_(4)/AC catalysts in cascade reactors.Our results strongly suggest that dehydrochlorination is an essential step in the coupling reaction,and the activation of acetylene and ethylene dichloride molecules requires different active sites that should be engineered in future work.展开更多
A systematic study on the structure sensitivity,host effect,and the deactivation mechanism of Ircatalyzed selective hydrogenation of 1,3-butadiene,a key process in the purification of alkadiene for the upgrading of C4...A systematic study on the structure sensitivity,host effect,and the deactivation mechanism of Ircatalyzed selective hydrogenation of 1,3-butadiene,a key process in the purification of alkadiene for the upgrading of C4 cut,is presented by coupling steady-state catalytic testing,in-depth characterization,kinetic evaluation,and density functional theory calculations.We reveal that:(i) 1,3-Butadiene hydrogenation on iridium is structure-sensitive with the optimal particle size of about 2 nm,and the H_(2) dissociation energy is a reliable activity descriptor;(ii) The nature of the NC hosts exerts a critical impact on the catalytic performance,and balanced nitrogen content and speciation seem key for the optimized performance;and (iii) Different deactivation mechanisms occur:fouling by coke deposition on the catalysts with a high N:C ratio (>1),and site blockage due to the competitive adsorption between 1-butene/cis-2-butene and 1,3-butadiene.These molecular insights provide valuable guidelines for the catalyst design in selective hydrogenations.展开更多
Synthesis of new carbon nanostructures with tunable properties is vital for precisely regulating electrochemical performance in the wide applications.Herein,we report a novel approach for the oxidative polymerization ...Synthesis of new carbon nanostructures with tunable properties is vital for precisely regulating electrochemical performance in the wide applications.Herein,we report a novel approach for the oxidative polymerization of N-and P-bearing copolymers from the self-assembly of three different monomers(aniline,pyrrole,and phytic acid),and further prepare the respective carbon nanostructures with relatively consistent N dopant(6.2%–8.0%,atom)and varying P concentrations(0.4%–2.8%,atom)via controllable pyrolysis.The impacts of phytic acid addition on the compositional,structural,and morphological evolution of the copolymers and the resulting nanocarbons are well studied through a spectrum of characterizations including N2 sorption,Fourier transform infrared spectroscopy,gel permeation chromatograph,scanning/transmission electron microscopy,and X-ray photoelectron spectroscopy.Gradual fragmentation of the nanosphere structures is evidenced with increasing addition of phytic acid,leading to different nanostructures from hollow nanospheres to 3D aggregates.Nanocarbons decorated with N and P dopants from pyrolysis are further utilized as anode materials in lithium-ion batteries,demonstrating enhanced electrochemical performance,i.e.,a reversible capacity of 380 mAhg^(-1)at 2 Ag^(-1)for NPC-0.5 during 200 cycles.The superior performance originates from the balanced porosity,and appropriate concentrations of P and pyrrolic N,thus pointing the direction for designing high-performance anode materials.展开更多
Green rusts with brucite-like layers of hydroxide intercalated with anions constitute a family of diverse precursors for the synthesis of iron oxides via dehydration,but precise structural control of the resulting oxi...Green rusts with brucite-like layers of hydroxide intercalated with anions constitute a family of diverse precursors for the synthesis of iron oxides via dehydration,but precise structural control of the resulting oxides with respect to the size and shape at the nanometer level remains challenging due to the easy oxidation of the ferrous species.Herein,we report a new synthetic strategy for the facile preparation of fibrous-like green rusts by using appropriate balancing anions(CO_(3)^(2-)and SO_(4)^(2-))in ethylene glycol to regulate the morphology.Depending on the type of the intercalating anion,the green rusts were converted into hematite with fibrous-or plate-like shapes upon thermal activation.When evaluated in the reaction of NO reduction by CO,these iron oxides showed a prominent shape-dependent catalytic behavior.The fibrous-like Fe_(2)O_(3)was much more catalytically active and structurally robust than the plate-like analogue.Combined spectroscopic and microscopic characterizations on the nanostructured iron oxides revealed that the superior performance of the fibrous-like Fe_(2)O_(3)stemmed from a facile Fe_(2)O_(3)/Fe_(3)O_(4)redox cycle and a higher density of active sites for NO activation.展开更多
β-FeOOH nanorods of 40 nm wide and 450 nm long were fabricated through precisely regulating the hydrolysis kinetics of Fe3＋ in polyethylene glycol and the concentration of C1- as the structure-directing agent. Detai...β-FeOOH nanorods of 40 nm wide and 450 nm long were fabricated through precisely regulating the hydrolysis kinetics of Fe3＋ in polyethylene glycol and the concentration of C1- as the structure-directing agent. Detailed structural and chemical analyses of the intermediates during the synthesis identified that the strong interaction between PEG and Fe3＋ modulated the hydrolysis kinetics of Fe3＋and prevented the aggregation of β-FeOOH nanorods; while C1- provided sufficient nucleation sites, stabilized the hollow channel of β-FeOOH, and more importantly induced the growth of the nanorods along [001] direction.展开更多
基金financial supports from the Zhejiang Normal University(YS304320035)the Natural Science Foundation of China(21603039)。
文摘Supported nickel catalysts are promising candidates for dry reforming of methane, but agglomeration of Ni^(0) and coke deposition hinder the industrial applications. Herein, we report a novel interface-directed synthetic approach to construct distinct metal ensembles by carefully tuning the compositions of the carriers. A Zr-Mn-Zn ternary oxide-supported Ni catalyst, together with the respective binary oxide-supported analogues, was synthesized by adopting a sequential co-precipitation and wetness impregnation method. Combined characterization techniques identify distinct catalyst models, including (i) conventional NiO nanoparticles with different sizes on Zr-Mn and Zr-Zn, and (ii) epitaxially growing NiO ensembles of a few nanometers thickness at the periphery of ZnO_(x) particles. These catalysts exhibit divergent responses in the catalytic testing, with the ternary oxide system significantly outperforming the binary analogues. The strong electronic interactions between Mn-Ni increase Ni dispersion and the activity while the stability is strengthened upon Zn addition. Both high activity, high selectivity, and remarkable stability are attained upon co-adding Mn and Zn. The interfaces between Ni and Zr-Mn-Zn rather than the physical contacts of individual oxide-supported analogues through mechanical mixing are keys for the outstanding performance.
基金supported by Zhejiang Normal University (YS304320035, YS304320036)
文摘Selective hydrogenation of 1,3‐butadiene is an essential process in the upgrading of the crude C4 cut from the petroleum chemical sector.Catalyst design is crucial to achieve a virtually alkadiene‐free product while avoiding over‐hydrogenating valuable olefins.In addition to the great industrial relevance,this demanding selectivity pattern renders 1,3‐butadiene hydrogenation a widely used model reaction to discriminate selective hydrogenation catalysts in academia.Nonetheless,critical reviews on the catalyst development are extremely lacking in literature.In this review,we aim to provide the reader an in‐depth overview of different catalyst families,particularly the precious metal‐based monometallic catalysts(Pd,Pt,and Au),developed in the last half century.The emphasis is placed on the development of new strategies to design high‐performance architectures,the establishment of structure‐performance relationships,and the reaction and deactivation mechanisms.Thrilling directions for future optimization of catalyst formulations and engineering aspect are also provided.
文摘Acetylene coupling with ethylene dichloride,which uses both coal and oil resources,is attractive for sustainable PVC manufacturing.Herein,highly active and stable carbon nitride‐based catalysts were developed by a novel pre‐oxidation‐pyrolysis process,affording unprecedented dehydrochlorination activity with good durability.The best‐performing system was further modified with different precious metals(Au,Pt,and Ru)to promote the hydrochlorination chemistry between the in‐situ formed hydrogen chloride and acetylene co‐feed.The presence of metal centers intensifies the hydrochlorination activity but weakens the dehydrochlorination ability due to competitive adsorption between the two reactants at the metal sites.Superior coupling performance was achieved over C_(3)N_(4)/AC and single‐atom Au/C_(3)N_(4)/AC catalysts in cascade reactors.Our results strongly suggest that dehydrochlorination is an essential step in the coupling reaction,and the activation of acetylene and ethylene dichloride molecules requires different active sites that should be engineered in future work.
基金Zhejiang Normal University for providing the financial support (YS304320035, YS304320036, ZZ323205020521005039)Financial support from the National Natural Science Foundation of China (NSFC, 21606199)+1 种基金the Science and Technology Department of Zhejiang Province (LGG20B060004)the National Key Research and Development Program of China (2021YFA1501800, 2021YFA1501801, 2021YFA1501802) are also gratefully acknowledged。
文摘A systematic study on the structure sensitivity,host effect,and the deactivation mechanism of Ircatalyzed selective hydrogenation of 1,3-butadiene,a key process in the purification of alkadiene for the upgrading of C4 cut,is presented by coupling steady-state catalytic testing,in-depth characterization,kinetic evaluation,and density functional theory calculations.We reveal that:(i) 1,3-Butadiene hydrogenation on iridium is structure-sensitive with the optimal particle size of about 2 nm,and the H_(2) dissociation energy is a reliable activity descriptor;(ii) The nature of the NC hosts exerts a critical impact on the catalytic performance,and balanced nitrogen content and speciation seem key for the optimized performance;and (iii) Different deactivation mechanisms occur:fouling by coke deposition on the catalysts with a high N:C ratio (>1),and site blockage due to the competitive adsorption between 1-butene/cis-2-butene and 1,3-butadiene.These molecular insights provide valuable guidelines for the catalyst design in selective hydrogenations.
基金support from Zhejiang Normal University(YS304320035,YS304320036)the National Key Research and Development Program of China(2016YFB0100100,2016YFA0200200)+5 种基金the National Natural Science Foundation of China(51872283,22075279,21805273,22005297,22005298)the Liaoning Revitalization Talents Program(XLYC1807153)the Funds for Local Science and Technology Development by the Central Government of Liaoning Province(2021JH6/10500112)Dalian Innovation Support Plan for High Level Talents(2019RT09)Dalian National Laboratory For Clean Energy(DNL),CAS,DNL Cooperation Fund,CAS(DNL201912,DNL201915)DICP(DICP ZZBS201708,DICP ZZBS201802,DICP I2020032).
文摘Synthesis of new carbon nanostructures with tunable properties is vital for precisely regulating electrochemical performance in the wide applications.Herein,we report a novel approach for the oxidative polymerization of N-and P-bearing copolymers from the self-assembly of three different monomers(aniline,pyrrole,and phytic acid),and further prepare the respective carbon nanostructures with relatively consistent N dopant(6.2%–8.0%,atom)and varying P concentrations(0.4%–2.8%,atom)via controllable pyrolysis.The impacts of phytic acid addition on the compositional,structural,and morphological evolution of the copolymers and the resulting nanocarbons are well studied through a spectrum of characterizations including N2 sorption,Fourier transform infrared spectroscopy,gel permeation chromatograph,scanning/transmission electron microscopy,and X-ray photoelectron spectroscopy.Gradual fragmentation of the nanosphere structures is evidenced with increasing addition of phytic acid,leading to different nanostructures from hollow nanospheres to 3D aggregates.Nanocarbons decorated with N and P dopants from pyrolysis are further utilized as anode materials in lithium-ion batteries,demonstrating enhanced electrochemical performance,i.e.,a reversible capacity of 380 mAhg^(-1)at 2 Ag^(-1)for NPC-0.5 during 200 cycles.The superior performance originates from the balanced porosity,and appropriate concentrations of P and pyrrolic N,thus pointing the direction for designing high-performance anode materials.
基金Zhejiang Normal University for providing the financial support(YS304320035)。
文摘Green rusts with brucite-like layers of hydroxide intercalated with anions constitute a family of diverse precursors for the synthesis of iron oxides via dehydration,but precise structural control of the resulting oxides with respect to the size and shape at the nanometer level remains challenging due to the easy oxidation of the ferrous species.Herein,we report a new synthetic strategy for the facile preparation of fibrous-like green rusts by using appropriate balancing anions(CO_(3)^(2-)and SO_(4)^(2-))in ethylene glycol to regulate the morphology.Depending on the type of the intercalating anion,the green rusts were converted into hematite with fibrous-or plate-like shapes upon thermal activation.When evaluated in the reaction of NO reduction by CO,these iron oxides showed a prominent shape-dependent catalytic behavior.The fibrous-like Fe_(2)O_(3)was much more catalytically active and structurally robust than the plate-like analogue.Combined spectroscopic and microscopic characterizations on the nanostructured iron oxides revealed that the superior performance of the fibrous-like Fe_(2)O_(3)stemmed from a facile Fe_(2)O_(3)/Fe_(3)O_(4)redox cycle and a higher density of active sites for NO activation.
基金supported by the National Natural Science Foundation of China (21025312, 21303193, 21321002)the National Key Basic Research Program of China (2013CB933100)
文摘β-FeOOH nanorods of 40 nm wide and 450 nm long were fabricated through precisely regulating the hydrolysis kinetics of Fe3＋ in polyethylene glycol and the concentration of C1- as the structure-directing agent. Detailed structural and chemical analyses of the intermediates during the synthesis identified that the strong interaction between PEG and Fe3＋ modulated the hydrolysis kinetics of Fe3＋and prevented the aggregation of β-FeOOH nanorods; while C1- provided sufficient nucleation sites, stabilized the hollow channel of β-FeOOH, and more importantly induced the growth of the nanorods along [001] direction.
