Metal atoms atomically dispersed on an inorganic metal‐based support compose a unique category of single atom catalysts(SACs)and have important applications in catalytic photoreduction reactions,including H_(2) evolu...Metal atoms atomically dispersed on an inorganic metal‐based support compose a unique category of single atom catalysts(SACs)and have important applications in catalytic photoreduction reactions,including H_(2) evolution reaction,CO_(2) reduction reaction,and N_(2) reduction reaction.In this minreview,we summarized the typical metal‐support interaction(M‐SI)patterns for successful anchoring of single‐atom metals on metallic compound supports.Subsequently,the contribution of the dispersed single metal atoms and M‐SI to photocatalytic reactions with improved activity,selectivity,and stability are highlighted,such as by accelerating charge transfer,regulating band structure of the support,acting as the reductive sites,and/or increasing catalytic selectivity.Finally,some challenges and perspectives of future development are proposed.We anticipate that this minireview will be a beneficial supplement for a comprehensive perception of metal‐based material supported SACs and their application in heterogeneous photo‐reductive catalysis.展开更多
The incorporation of Pt into an iron-nitrogen-carbon(Fe NC)catalyst for the oxygen reduction reaction(ORR)was recently shown to enhance catalyst stability without Pt directly contributing to the ORR activity.However,t...The incorporation of Pt into an iron-nitrogen-carbon(Fe NC)catalyst for the oxygen reduction reaction(ORR)was recently shown to enhance catalyst stability without Pt directly contributing to the ORR activity.However,the mechanistic origin of this stabilisation remained obscure.It is established herein with rotating ring disc experiments that the side product,H_(2)O_(2),which is known to damage FeNC catalysts,is suppressed by the presence of Pt.The formation of reactive oxygen species is additionally inhibited,independent of intrinsic H_(2)O_(2) formation,as determined by electron paramagnetic resonance.Transmission electron microscopy identifies an oxidised Fe-rich layer covering the Pt particles,thus explaining the inactivity of the latter towards the ORR.These insights develop understanding of Fe NC degradation mechanisms during ORR catalysis,and crucially establish the required properties of a precious metal free protective catalyst to improve Fe NC stability in acidic media.展开更多
The Ru/Al2O3 catalysts modified with metal oxide （K20 and La2O3） were prepared v/a incipient wetness impregnation method from RuCl3.nH2O mixed with nitrate loading on Al2O3 support. The activity of catalysts was eva...The Ru/Al2O3 catalysts modified with metal oxide （K20 and La2O3） were prepared v/a incipient wetness impregnation method from RuCl3.nH2O mixed with nitrate loading on Al2O3 support. The activity of catalysts was evaluated under simulative conditions for the preferential oxidation of CO （CO-PROX） from the hydrogen-rich gas streams produced by reforming gas, and the performances of catalysts were investigated by XRD and TPR. The results showed that the activity temperature of the modified catalysts Ru-K20/Al2O3 and Ru-La2O3/Al2O3 were lowered approximately 30℃ compared with pure Ru/Al2O3, and the activity temperature range was widened. The conversion of CO on Ru-K20/Al2O3 and Ru-La2O3/Al2O3 was above 99% at 140-160℃, suitable to remove CO in a hydrogen-rich gas and the selectivity of Ru-La2O3/Al2O3 was higher than that of Ru-K2O/Al2O3in the active temperature range. Slight methanation reaction was detected at 220℃ and above.展开更多
Surface properties （viz. surface area, basicity/base strength distribution, and crystal phases） of alkali metal doped CaO （alkali metal/Ca= 0.1 and 0.4） catalysts and their catalytic activity/selectivity in oxidat...Surface properties （viz. surface area, basicity/base strength distribution, and crystal phases） of alkali metal doped CaO （alkali metal/Ca= 0.1 and 0.4） catalysts and their catalytic activity/selectivity in oxidative coupling of methane （OCM） to higher hydrocarbons at different reaction conditions （viz. temperature, 700 and 750 ℃; CH4/O2 ratio, 4.0 and 8.0 and space velocity, 5140-20550 cm^3 ·g^-1·h^-1） have been investigated. The influence of catalyst calcination temperature on the activity/selectivity has also been investigated. The surface properties （viz. surface area, basicity/base strength distribution） and catalytic activity/selectivity of the alkali metal doped CaO catalysts are strongly influenced by the alkali metal promoter and its concentration in the alkali metal doped CaO catalysts. An addition of alkali metal promoter to CaO results in a large decrease in the surface area but a large increase in the surface basicity （strong basic sites） and the C2＋ selectivity and yield of the catalysts in the OCM process. The activity and selectivity are strongly influenced by the catalyst calcination temperature. No direct relationship between surface basicity and catalytic activity/selectivity has been observed. Among the alkali metal doped CaO catalysts, Na-CaO （Na/Ca = 0.1, before calcination） catalyst （calcined at 750 ℃）, showed best performance （C2＋ selectivity of 68.8% with 24.7% methane conversion）, whereas the poorest performance was shown by the Rb-CaO catalyst in the OCM process.展开更多
CoCu/TiO_2 catalysts promoted using alkali metals（Li, Na, K, Rb, and Cs） were prepared by the homogeneous deposition-precipitation method followed by the incipient wetness impregnation method. The influences of the ...CoCu/TiO_2 catalysts promoted using alkali metals（Li, Na, K, Rb, and Cs） were prepared by the homogeneous deposition-precipitation method followed by the incipient wetness impregnation method. The influences of the alkali metals on the physicochemical properties of the CoCu/TiO_2 catalysts and the catalytic performance for CO_2 hydrogenation to long-chain hydrocarbons（C_（5＋））were investigated in this work. According to the characterization of the catalysts based on X-ray photoelectron spectroscopy, X-ray diffraction, CO_2 temperature-programmed desorption（TPD）, and H_2-TPD, the introduction of alkali metals could increase the CO_2 adsorption and decrease the H_2 chemisorption, which could suppress the formation of CH_4, enhance the production of C_（5＋）, and decrease the hydrogenation activity. Among all the promoters, the Na-modified CoCu/TiO_2 catalyst provided the maximum C_（5＋） yield of 5.4%, with a CO_2 conversion of 18.4% and C_（5＋） selectivity of42.1%, because it showed the strongest basicity and a slight decrease in the amount of H_2 desorption;it also exhibited excellent catalytic stability of more than 200 h.展开更多
The use of silver metal for hydrodeoxygenation(HDO) applications is scarce and different studies have indicated of its varying HDO activity. Several computational studies have reported of silver having almost zero tur...The use of silver metal for hydrodeoxygenation(HDO) applications is scarce and different studies have indicated of its varying HDO activity. Several computational studies have reported of silver having almost zero turnover frequency for HDO owing to its high C\\O bond breaking energy barrier and low carbon and oxygen binding energies.Herein this work, titania supported silver catalysts were synthesized and firstly used to examine its phenol HDO activity via experimental reaction runs. BET, XRD, FESEM, TEM, EDX, ICP–OES, Pyridine-FTIR, NH_3-TPD and H_2-TPD analyses were done to investigate its physicochemical properties. Phenomena of hydrogen spillover and metal–acid site synergy were examined in this study. With the aid of TiO_2 reducible support, hydrogen spillover and metal–acid site interactions were observed to a certain extent but were not as superior as other Pt, Pd, Ni-based catalysts used in other HDO studies. The experimental findings showed that Ag/TiO_2 catalyst has mediocre phenol conversion but high benzene selectivity which confirms the explanation from other computational studies.展开更多
High cost has undoubtedly become the biggest obstacle to the commercialization of proton exchange membrane fuel cells(PEMFCs),in which Pt-based catalysts employed in the cathodic catalyst layer(CCL)account for the maj...High cost has undoubtedly become the biggest obstacle to the commercialization of proton exchange membrane fuel cells(PEMFCs),in which Pt-based catalysts employed in the cathodic catalyst layer(CCL)account for the major portion of the cost.Although nonprecious metal catalysts(NPMCs)show appreciable activity and stability in the oxygen reduction reaction(ORR),the performance of fuel cells based on NPMCs remains unsatisfactory compared to those using Pt-based CCL.Therefore,most studies on NPMC-based fuel cells focus on developing highly active catalysts rather than facilitating oxygen transport.In this work,the oxygen transport behavior in CCLs based on highly active Fe-N-C catalysts is comprehensively explored through the elaborate design of two types of membrane electrode structures,one containing low-Pt-based CCL and NPMCbased dummy catalyst layer(DCL)and the other containing only the NPMC-based CCL.Using Zn-N-C based DCLs of different thickness,the bulk oxygen transport resistance at the unit thickness in NPMC-based CCL was quantified via the limiting current method combined with linear fitting analysis.Then,the local and bulk resistances in NPMC-based CCLs were quantified via the limiting current method and scanning electron microscopy,respectively.Results show that the ratios of local and bulk oxygen transport resistances in NPMCbased CCL are 80%and 20%,respectively,and that an enhancement of local oxygen transport is critical to greatly improve the performance of NPMC-based PEMFCs.Furthermore,the activity of active sites per unit in NPMCbased CCLs was determined to be lower than that in the Pt-based CCL,thus explaining worse cell performance of NPMC-based membrane electrode assemblys(MEAs).It is believed that the development of NPMC-based PEMFCs should proceed not only through the design of catalysts with higher activity but also through the improvement of oxygen transport in the CCL.展开更多
Seeking effective solutions to control and mitigate the interaction between drilling fluids and clay formations has been a challenge for many years, and various shale inhibitors have shown excellent results in problem...Seeking effective solutions to control and mitigate the interaction between drilling fluids and clay formations has been a challenge for many years, and various shale inhibitors have shown excellent results in problematic shale formations around the world. Herein, the hyperbranched polyamine (HBPA) inhibitor with a higher ratio of amine groups and obvious tendentiousness in protonation was successfully synthesized from ethylenediamine, acryloyl chloride and aziridine by five steps, in which the metal-organic framework (MOF) was employed as a catalyst for ring-open polycondensation (ROP). The structure and purity were confirmed by nuclear magnetic resonance hydrogen spectroscopy and high-performance liquid chromatography (HPLC) respectively. The HBPA displays more excellent performance than EDA and KCl widely applied in the oil field. After aging at 80°C and 180°C, the YP of a slurry system containing 25 wt.% bentonite and 2 wt.% HBPA are just 8.5 Pa and 5.5 Pa (wt.%: percentage of mass), respectively. The swelling lengths of 2 wt.% HBPA are estimated to be 1.78 mm, which falls by 70% compared with that of freshwater. Under a hot rolling aging temperature of 180°C, the HBPA system demonstrates a significant inhibition with more than 85% shale cuttings recovery rate and is superior to conventional EDA and KCl. Mechanism analysis further validates that the HBPA can help to increase the zeta potential.展开更多
A non-precious metal catalyst MnHMTA/C to oxygen reduction reaction was prepared by py- rolyzing a precursor from manganese chloride, hexamethylenetetramine and acetylene black in nitrogen gas atmosphere. The effect o...A non-precious metal catalyst MnHMTA/C to oxygen reduction reaction was prepared by py- rolyzing a precursor from manganese chloride, hexamethylenetetramine and acetylene black in nitrogen gas atmosphere. The effect of heat treatment temperature and flowing of nitrogen gas were investigated. A catalyst with the highest activity can be obtained at 700 ℃. Mn（Ⅱ） ion was changed to MnO in heat treatment, which improved the catalytic activity of the catalyst. Hexamethylenetetramine takes part in the formation of active site of the catalyst as its decomposed gases. The flowing of protective gas takes the decomposed gases out of the tube furnace and brings negative effect on the catalytic activity of the MnHMTA/C catalyst.展开更多
Understanding of the oxygen reduction reaction(ORR)mechanism for single atom catalysts is pivotal for the rational design of non-precious metal cathode materials and the commercialization of fuel cells.Herein,a series...Understanding of the oxygen reduction reaction(ORR)mechanism for single atom catalysts is pivotal for the rational design of non-precious metal cathode materials and the commercialization of fuel cells.Herein,a series of non-precious metal electrocatalysts based on nitrogen-doped bimetallic(Fe and Co)carbide were modeled by density functional theory calculations to predict the corresponding reaction pathways.The study elucidated prior oxygen adsorption on the Fe atom in the dual site and the modifier role of Co atoms to tune the electronic structures of Fe.The reaction activity was highly correlated with the bimetallic center and the coordination environment of the adjacent nitrogen.Interestingly,the preadsorption of*OH resulted in the apparent change of metal atoms'electronic states with the d-band center shifting toward the Fermi level,thereby boosting reaction activity.The result should help promote the fundamental understanding of active sites in ORR catalysts and provide an effective approach to the design of highly efficient ORR catalysts on an atomic scale.展开更多
Due to larger atom utilization,unique electronic properties and unsaturated coordination,atomically dispersed non-precious metal catalysts with outstanding performances have received great attention in electrocatalysi...Due to larger atom utilization,unique electronic properties and unsaturated coordination,atomically dispersed non-precious metal catalysts with outstanding performances have received great attention in electrocatalysis.Considering the challenge of serious aggregation,rational synthesis of an atomic catalyst with good dispersion of atoms is paramount to the development of these catalysts.Herein,we report an enhanced confinement strategy to synthesize a catalyst comprised of atomically dispersed Fe supported on porous nitrogen-doped graphitic carbon from the novel and more cross-linkable Melamine-Glyoxal Resin.Densified isolated grid trapping,excessive melamine restricting,and nitrogen anchoring are strongly combined to ensure the final atomic-level dispersion of metal atoms.Experimental studies revealed enhanced kinetics of the obtained catalyst towards oxygen reduction reaction(ORR).This catalytic activity originates from the highly active surface with atomically dispersed iron sites as well as the multi-level three-dimensional structure with fast mass and electron transfer.The enhanced confinement strategy endows the resin-derived atomic catalyst with a great prospect to develop for commercialization in future.展开更多
Nano-sized γ-alumina （γ-Al2O3） was first prepared by a precipitation method. Then, active component of cobalt and a series of alkaline- earth metal promoters or nickel （Ni） with different contents were loaded on...Nano-sized γ-alumina （γ-Al2O3） was first prepared by a precipitation method. Then, active component of cobalt and a series of alkaline- earth metal promoters or nickel （Ni） with different contents were loaded on the γ-Al2O3 support. The catalysts were characterized by N2 adsorption-desorption, X-ray diffraction （XRD） and thermogravimetry analysis （TGA）. The activity and selectivity of the catalysts in catalytic partial oxidation （CPO） of methane have been compared with Co/γ-Al2O3, and it is found that the catalytic activity, selectivity, and stability are enhanced by the addition of alkaline-earth metals and nickel. The optimal loadings of strontium （Sr） and Ni were 6 and 4 wt%, respectively. This finding will be helpful in designing the trimetallic Co-Ni-Sr/γ-Al2O3 catalysts with high performance in CPO of methane展开更多
Non-precious metal single-atom catalysts(NPM-SACs)with unique electronic structures and coordination environments have gained much attention in electrocatalysis owing to their low cost,high atomic utilization,and high...Non-precious metal single-atom catalysts(NPM-SACs)with unique electronic structures and coordination environments have gained much attention in electrocatalysis owing to their low cost,high atomic utilization,and high performance.NPM-SACs on carbon support(NPM-SACs/CS)are promising because of the carbon substrate with a large surface area,excellent electrical conductivity,and high chemical stability.This review provides an overview of recent developments in NPM-SACs/CS for the electrocatalytic field.First,the state-of-the-art synthesis methods and advanced characterization techniques of NPM-SACs/CS are discussed in detail.Then,the structural adjustment strategy of NPM-SACs/CS for optimizing electrocatalytic performance is introduced concisely.Furthermore,we provide a comprehensive summary of recent advances in developing NPM-SACs/CS for important electrochemical reactions,including carbon dioxide reduction reaction,hydrogen evolution reaction,oxygen evolution reaction,oxygen reduction reaction,and nitrogen reduction reaction.In the end,the existing challenges and future opportunities of NPM-SACs/CS in the electrocatalytic field are highlighted.展开更多
Chloranil through condensation reaction with vicinal diamine such as diaminomaleonitrile produced heterocyclic monomer, p-benzoquinonebis[2,3-b; 2＇,3＇-b＇]pyrazine-5,6-dinitrile. The tetranitrile monomer was cyclo-t...Chloranil through condensation reaction with vicinal diamine such as diaminomaleonitrile produced heterocyclic monomer, p-benzoquinonebis[2,3-b; 2＇,3＇-b＇]pyrazine-5,6-dinitrile. The tetranitrile monomer was cyclo-tetramerised using lithium/pentanol and acetic acid affording the corresponding tetrap-benzoquinone bis[2,3-b; 2＇,3＇-b＇]pyrazinoporphyrazine）]- based network polymer （2H-Pz）. The tetranitril monomer was cyclo-tetramerised using metal salt and quinoline affording the corresponding porphyrazinato-metal II-based network polymers （M-Pz）, M = Co, Ni or Cu. Elemental analytical results, IR and NMR spectral data of the prepared molecules are consistent with their assigned formulations. Molecular masses and metal contents of the synthesized polymers proved to be of high molecular masses which confirm the efficiency of tetramerization polymerization and complexation reactions. The prepared pyrazinoporphyrazines were used as efficient catalysts for the oxidation of thiophenol and benzylthiol to their disulfides in the presence of air atmosphere. The results of oxidation of thiophenol and benzylthiol show that after 15 min the maximum yield of the corresponding disulfides reached 95%, 91%, respectively.展开更多
A non-precious metal catalyst CoMe]C for the oxygen reduction reaction is prepared by heat-treating a mechanical mixture of carbon black, melamine and cobalt chloride at 600 under nitrogen atmosphere for 2 h. The cata...A non-precious metal catalyst CoMe]C for the oxygen reduction reaction is prepared by heat-treating a mechanical mixture of carbon black, melamine and cobalt chloride at 600 under nitrogen atmosphere for 2 h. The catalytic activity of CoMe/C is characterized by the electrochemical linear sweep voltammetry technique. The onset reduction potential of the catalyst is 0.55 V （vs. SCE） at a scanning rate of 5 mV/s in 0.5 mol/L H2SO4 solution. The formation of the ORR activity sites of CoMe/C is facilitated by metallic β- cobalt.展开更多
Modifying solid catalysts with an ionic liquid layer is an effective approach for boosting the performance of both Pt-based and non-precious metal catalysts toward the oxygen reduction reaction. While most studies ope...Modifying solid catalysts with an ionic liquid layer is an effective approach for boosting the performance of both Pt-based and non-precious metal catalysts toward the oxygen reduction reaction. While most studies operated at room temperature it remains unclear whether the IL-associated boosting effect can be maintained at elevated temperature, which is of high relevance for practical applications in low temperature fuel cells. Herein, Fe-N-C catalysts were modified by introducing small amounts of hydrophobic ionic liquid, resulting in boosted electrocatalytic activity towards the alkaline oxygen reduction reaction at room temperature. It is demonstrated that the boosting effect can be maintained and even strengthened when increasing the electrolyte temperature up to 70℃. These findings show for the first time that the incorporation of ionic liquid is a suited method to obtain advanced noble metal-free electrocatalysts that can be applied at operating temperature condition.展开更多
文摘Metal atoms atomically dispersed on an inorganic metal‐based support compose a unique category of single atom catalysts(SACs)and have important applications in catalytic photoreduction reactions,including H_(2) evolution reaction,CO_(2) reduction reaction,and N_(2) reduction reaction.In this minreview,we summarized the typical metal‐support interaction(M‐SI)patterns for successful anchoring of single‐atom metals on metallic compound supports.Subsequently,the contribution of the dispersed single metal atoms and M‐SI to photocatalytic reactions with improved activity,selectivity,and stability are highlighted,such as by accelerating charge transfer,regulating band structure of the support,acting as the reductive sites,and/or increasing catalytic selectivity.Finally,some challenges and perspectives of future development are proposed.We anticipate that this minireview will be a beneficial supplement for a comprehensive perception of metal‐based material supported SACs and their application in heterogeneous photo‐reductive catalysis.
基金a fellowship from the Alexander von Humboldt foundation。
文摘The incorporation of Pt into an iron-nitrogen-carbon(Fe NC)catalyst for the oxygen reduction reaction(ORR)was recently shown to enhance catalyst stability without Pt directly contributing to the ORR activity.However,the mechanistic origin of this stabilisation remained obscure.It is established herein with rotating ring disc experiments that the side product,H_(2)O_(2),which is known to damage FeNC catalysts,is suppressed by the presence of Pt.The formation of reactive oxygen species is additionally inhibited,independent of intrinsic H_(2)O_(2) formation,as determined by electron paramagnetic resonance.Transmission electron microscopy identifies an oxidised Fe-rich layer covering the Pt particles,thus explaining the inactivity of the latter towards the ORR.These insights develop understanding of Fe NC degradation mechanisms during ORR catalysis,and crucially establish the required properties of a precious metal free protective catalyst to improve Fe NC stability in acidic media.
基金the National Natural Science Foundation of China(20576023)the Guangdong Province Natural Science Foundation (06025660)
文摘The Ru/Al2O3 catalysts modified with metal oxide （K20 and La2O3） were prepared v/a incipient wetness impregnation method from RuCl3.nH2O mixed with nitrate loading on Al2O3 support. The activity of catalysts was evaluated under simulative conditions for the preferential oxidation of CO （CO-PROX） from the hydrogen-rich gas streams produced by reforming gas, and the performances of catalysts were investigated by XRD and TPR. The results showed that the activity temperature of the modified catalysts Ru-K20/Al2O3 and Ru-La2O3/Al2O3 were lowered approximately 30℃ compared with pure Ru/Al2O3, and the activity temperature range was widened. The conversion of CO on Ru-K20/Al2O3 and Ru-La2O3/Al2O3 was above 99% at 140-160℃, suitable to remove CO in a hydrogen-rich gas and the selectivity of Ru-La2O3/Al2O3 was higher than that of Ru-K2O/Al2O3in the active temperature range. Slight methanation reaction was detected at 220℃ and above.
文摘Surface properties （viz. surface area, basicity/base strength distribution, and crystal phases） of alkali metal doped CaO （alkali metal/Ca= 0.1 and 0.4） catalysts and their catalytic activity/selectivity in oxidative coupling of methane （OCM） to higher hydrocarbons at different reaction conditions （viz. temperature, 700 and 750 ℃; CH4/O2 ratio, 4.0 and 8.0 and space velocity, 5140-20550 cm^3 ·g^-1·h^-1） have been investigated. The influence of catalyst calcination temperature on the activity/selectivity has also been investigated. The surface properties （viz. surface area, basicity/base strength distribution） and catalytic activity/selectivity of the alkali metal doped CaO catalysts are strongly influenced by the alkali metal promoter and its concentration in the alkali metal doped CaO catalysts. An addition of alkali metal promoter to CaO results in a large decrease in the surface area but a large increase in the surface basicity （strong basic sites） and the C2＋ selectivity and yield of the catalysts in the OCM process. The activity and selectivity are strongly influenced by the catalyst calcination temperature. No direct relationship between surface basicity and catalytic activity/selectivity has been observed. Among the alkali metal doped CaO catalysts, Na-CaO （Na/Ca = 0.1, before calcination） catalyst （calcined at 750 ℃）, showed best performance （C2＋ selectivity of 68.8% with 24.7% methane conversion）, whereas the poorest performance was shown by the Rb-CaO catalyst in the OCM process.
文摘CoCu/TiO_2 catalysts promoted using alkali metals（Li, Na, K, Rb, and Cs） were prepared by the homogeneous deposition-precipitation method followed by the incipient wetness impregnation method. The influences of the alkali metals on the physicochemical properties of the CoCu/TiO_2 catalysts and the catalytic performance for CO_2 hydrogenation to long-chain hydrocarbons（C_（5＋））were investigated in this work. According to the characterization of the catalysts based on X-ray photoelectron spectroscopy, X-ray diffraction, CO_2 temperature-programmed desorption（TPD）, and H_2-TPD, the introduction of alkali metals could increase the CO_2 adsorption and decrease the H_2 chemisorption, which could suppress the formation of CH_4, enhance the production of C_（5＋）, and decrease the hydrogenation activity. Among all the promoters, the Na-modified CoCu/TiO_2 catalyst provided the maximum C_（5＋） yield of 5.4%, with a CO_2 conversion of 18.4% and C_（5＋） selectivity of42.1%, because it showed the strongest basicity and a slight decrease in the amount of H_2 desorption;it also exhibited excellent catalytic stability of more than 200 h.
基金GSP-MOHE,University of Malaya for fully funding this study through the project number "MO008-2015"Ministry of Higher Education of Malaysia (MOHE) for MyBrain15 (MyPhD) programIPPP for project "PG081-2016A"
文摘The use of silver metal for hydrodeoxygenation(HDO) applications is scarce and different studies have indicated of its varying HDO activity. Several computational studies have reported of silver having almost zero turnover frequency for HDO owing to its high C\\O bond breaking energy barrier and low carbon and oxygen binding energies.Herein this work, titania supported silver catalysts were synthesized and firstly used to examine its phenol HDO activity via experimental reaction runs. BET, XRD, FESEM, TEM, EDX, ICP–OES, Pyridine-FTIR, NH_3-TPD and H_2-TPD analyses were done to investigate its physicochemical properties. Phenomena of hydrogen spillover and metal–acid site synergy were examined in this study. With the aid of TiO_2 reducible support, hydrogen spillover and metal–acid site interactions were observed to a certain extent but were not as superior as other Pt, Pd, Ni-based catalysts used in other HDO studies. The experimental findings showed that Ag/TiO_2 catalyst has mediocre phenol conversion but high benzene selectivity which confirms the explanation from other computational studies.
基金the National Key R&D Program of China(Grant No.2021YFB4001303)the National Natural Science Foundation of China(Grant No.21975157)。
文摘High cost has undoubtedly become the biggest obstacle to the commercialization of proton exchange membrane fuel cells(PEMFCs),in which Pt-based catalysts employed in the cathodic catalyst layer(CCL)account for the major portion of the cost.Although nonprecious metal catalysts(NPMCs)show appreciable activity and stability in the oxygen reduction reaction(ORR),the performance of fuel cells based on NPMCs remains unsatisfactory compared to those using Pt-based CCL.Therefore,most studies on NPMC-based fuel cells focus on developing highly active catalysts rather than facilitating oxygen transport.In this work,the oxygen transport behavior in CCLs based on highly active Fe-N-C catalysts is comprehensively explored through the elaborate design of two types of membrane electrode structures,one containing low-Pt-based CCL and NPMCbased dummy catalyst layer(DCL)and the other containing only the NPMC-based CCL.Using Zn-N-C based DCLs of different thickness,the bulk oxygen transport resistance at the unit thickness in NPMC-based CCL was quantified via the limiting current method combined with linear fitting analysis.Then,the local and bulk resistances in NPMC-based CCLs were quantified via the limiting current method and scanning electron microscopy,respectively.Results show that the ratios of local and bulk oxygen transport resistances in NPMCbased CCL are 80%and 20%,respectively,and that an enhancement of local oxygen transport is critical to greatly improve the performance of NPMC-based PEMFCs.Furthermore,the activity of active sites per unit in NPMCbased CCLs was determined to be lower than that in the Pt-based CCL,thus explaining worse cell performance of NPMC-based membrane electrode assemblys(MEAs).It is believed that the development of NPMC-based PEMFCs should proceed not only through the design of catalysts with higher activity but also through the improvement of oxygen transport in the CCL.
文摘Seeking effective solutions to control and mitigate the interaction between drilling fluids and clay formations has been a challenge for many years, and various shale inhibitors have shown excellent results in problematic shale formations around the world. Herein, the hyperbranched polyamine (HBPA) inhibitor with a higher ratio of amine groups and obvious tendentiousness in protonation was successfully synthesized from ethylenediamine, acryloyl chloride and aziridine by five steps, in which the metal-organic framework (MOF) was employed as a catalyst for ring-open polycondensation (ROP). The structure and purity were confirmed by nuclear magnetic resonance hydrogen spectroscopy and high-performance liquid chromatography (HPLC) respectively. The HBPA displays more excellent performance than EDA and KCl widely applied in the oil field. After aging at 80°C and 180°C, the YP of a slurry system containing 25 wt.% bentonite and 2 wt.% HBPA are just 8.5 Pa and 5.5 Pa (wt.%: percentage of mass), respectively. The swelling lengths of 2 wt.% HBPA are estimated to be 1.78 mm, which falls by 70% compared with that of freshwater. Under a hot rolling aging temperature of 180°C, the HBPA system demonstrates a significant inhibition with more than 85% shale cuttings recovery rate and is superior to conventional EDA and KCl. Mechanism analysis further validates that the HBPA can help to increase the zeta potential.
文摘A non-precious metal catalyst MnHMTA/C to oxygen reduction reaction was prepared by py- rolyzing a precursor from manganese chloride, hexamethylenetetramine and acetylene black in nitrogen gas atmosphere. The effect of heat treatment temperature and flowing of nitrogen gas were investigated. A catalyst with the highest activity can be obtained at 700 ℃. Mn（Ⅱ） ion was changed to MnO in heat treatment, which improved the catalytic activity of the catalyst. Hexamethylenetetramine takes part in the formation of active site of the catalyst as its decomposed gases. The flowing of protective gas takes the decomposed gases out of the tube furnace and brings negative effect on the catalytic activity of the MnHMTA/C catalyst.
基金the Joint Fund of the National Natural Science Foundation of China(U1732267).
文摘Understanding of the oxygen reduction reaction(ORR)mechanism for single atom catalysts is pivotal for the rational design of non-precious metal cathode materials and the commercialization of fuel cells.Herein,a series of non-precious metal electrocatalysts based on nitrogen-doped bimetallic(Fe and Co)carbide were modeled by density functional theory calculations to predict the corresponding reaction pathways.The study elucidated prior oxygen adsorption on the Fe atom in the dual site and the modifier role of Co atoms to tune the electronic structures of Fe.The reaction activity was highly correlated with the bimetallic center and the coordination environment of the adjacent nitrogen.Interestingly,the preadsorption of*OH resulted in the apparent change of metal atoms'electronic states with the d-band center shifting toward the Fermi level,thereby boosting reaction activity.The result should help promote the fundamental understanding of active sites in ORR catalysts and provide an effective approach to the design of highly efficient ORR catalysts on an atomic scale.
基金financially supported by the Hebei Province Natural Science Foundation Innovation Group Project(B2021203016)the National Natural Science Foundation of China(51674221 and 51704261)+1 种基金the Provincial Graduate Innovation Assistant Project of Yanshan University(023000309)partially supported by the ARC Future Fellowship(FT180100705)of Australia。
文摘Due to larger atom utilization,unique electronic properties and unsaturated coordination,atomically dispersed non-precious metal catalysts with outstanding performances have received great attention in electrocatalysis.Considering the challenge of serious aggregation,rational synthesis of an atomic catalyst with good dispersion of atoms is paramount to the development of these catalysts.Herein,we report an enhanced confinement strategy to synthesize a catalyst comprised of atomically dispersed Fe supported on porous nitrogen-doped graphitic carbon from the novel and more cross-linkable Melamine-Glyoxal Resin.Densified isolated grid trapping,excessive melamine restricting,and nitrogen anchoring are strongly combined to ensure the final atomic-level dispersion of metal atoms.Experimental studies revealed enhanced kinetics of the obtained catalyst towards oxygen reduction reaction(ORR).This catalytic activity originates from the highly active surface with atomically dispersed iron sites as well as the multi-level three-dimensional structure with fast mass and electron transfer.The enhanced confinement strategy endows the resin-derived atomic catalyst with a great prospect to develop for commercialization in future.
基金supported by the Open Foundation of State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University (No.200906)the Natural Science Foundation of Jiangxi Province (No.2010GZH0048)+1 种基金the National Natural Science Foundation of China (No. 21067004)the Young Science Foundation of Jiangxi Province Education Office (No. GJJ10150)
文摘Nano-sized γ-alumina （γ-Al2O3） was first prepared by a precipitation method. Then, active component of cobalt and a series of alkaline- earth metal promoters or nickel （Ni） with different contents were loaded on the γ-Al2O3 support. The catalysts were characterized by N2 adsorption-desorption, X-ray diffraction （XRD） and thermogravimetry analysis （TGA）. The activity and selectivity of the catalysts in catalytic partial oxidation （CPO） of methane have been compared with Co/γ-Al2O3, and it is found that the catalytic activity, selectivity, and stability are enhanced by the addition of alkaline-earth metals and nickel. The optimal loadings of strontium （Sr） and Ni were 6 and 4 wt%, respectively. This finding will be helpful in designing the trimetallic Co-Ni-Sr/γ-Al2O3 catalysts with high performance in CPO of methane
基金support from the China Postdoctoral Science Foundation(2022M711553).Y.W.would like to acknowledge the support from the National Natural Science Foundation of China(22171132)the Innovation Fund from Nanjing University(020514913419)+5 种基金the Program for Innovative Talents and Entrepreneurs in Jiangsu(020513006012 and 020513006014),and the National Key R&D Program of China(2002YFB3607000).W.Z.would like to acknowledge the support from the National Natural Science Foundation of China(22176086)Natural Science Foundation of Jiangsu Province(BK20210189)State Key Laboratory of Pollution Control and Resource Reuse(PCRR-ZZ-202106)the Fundamental Research Funds for the Central Universities(021114380183,021114380189 and 021114380199)the Research Funds from the Nanjing Science and Technology Innovation Project for Chinese Scholars Studying Abroad(13006003)the Research Funds from Frontiers Science Center for Critical Earth Material Cycling of Nanjing University,and Research Funds for Jiangsu Distinguished Professor.Y.L.would like to thank the support from the Washington State University startup fund.
文摘Non-precious metal single-atom catalysts(NPM-SACs)with unique electronic structures and coordination environments have gained much attention in electrocatalysis owing to their low cost,high atomic utilization,and high performance.NPM-SACs on carbon support(NPM-SACs/CS)are promising because of the carbon substrate with a large surface area,excellent electrical conductivity,and high chemical stability.This review provides an overview of recent developments in NPM-SACs/CS for the electrocatalytic field.First,the state-of-the-art synthesis methods and advanced characterization techniques of NPM-SACs/CS are discussed in detail.Then,the structural adjustment strategy of NPM-SACs/CS for optimizing electrocatalytic performance is introduced concisely.Furthermore,we provide a comprehensive summary of recent advances in developing NPM-SACs/CS for important electrochemical reactions,including carbon dioxide reduction reaction,hydrogen evolution reaction,oxygen evolution reaction,oxygen reduction reaction,and nitrogen reduction reaction.In the end,the existing challenges and future opportunities of NPM-SACs/CS in the electrocatalytic field are highlighted.
文摘Chloranil through condensation reaction with vicinal diamine such as diaminomaleonitrile produced heterocyclic monomer, p-benzoquinonebis[2,3-b; 2＇,3＇-b＇]pyrazine-5,6-dinitrile. The tetranitrile monomer was cyclo-tetramerised using lithium/pentanol and acetic acid affording the corresponding tetrap-benzoquinone bis[2,3-b; 2＇,3＇-b＇]pyrazinoporphyrazine）]- based network polymer （2H-Pz）. The tetranitril monomer was cyclo-tetramerised using metal salt and quinoline affording the corresponding porphyrazinato-metal II-based network polymers （M-Pz）, M = Co, Ni or Cu. Elemental analytical results, IR and NMR spectral data of the prepared molecules are consistent with their assigned formulations. Molecular masses and metal contents of the synthesized polymers proved to be of high molecular masses which confirm the efficiency of tetramerization polymerization and complexation reactions. The prepared pyrazinoporphyrazines were used as efficient catalysts for the oxidation of thiophenol and benzylthiol to their disulfides in the presence of air atmosphere. The results of oxidation of thiophenol and benzylthiol show that after 15 min the maximum yield of the corresponding disulfides reached 95%, 91%, respectively.
基金supported by the Fundamental Research Funds for the Central Universities (No. CDJXS12220002)the Specialized Research Fund for the Doctoral Program of Sichuan University of Science and Engineering (No. 2012RC16)+2 种基金the Opening Project of Key Laboratory of Green Catalysis of Sichuan Institutes of High Education (No. LYJ1206)the National Undergraduate Innovation Training Project (No. 1110611046)Discipline Construction Project of Sichuan University of Science and Engineering
文摘A non-precious metal catalyst CoMe]C for the oxygen reduction reaction is prepared by heat-treating a mechanical mixture of carbon black, melamine and cobalt chloride at 600 under nitrogen atmosphere for 2 h. The catalytic activity of CoMe/C is characterized by the electrochemical linear sweep voltammetry technique. The onset reduction potential of the catalyst is 0.55 V （vs. SCE） at a scanning rate of 5 mV/s in 0.5 mol/L H2SO4 solution. The formation of the ORR activity sites of CoMe/C is facilitated by metallic β- cobalt.
基金funding from the European Research Council (ERC) under the European Union’s Horizon 2020 Research and Innovation Program (Grant No. 681719)the German Research Foundation (Grant No.GSC1070) for financial support。
文摘Modifying solid catalysts with an ionic liquid layer is an effective approach for boosting the performance of both Pt-based and non-precious metal catalysts toward the oxygen reduction reaction. While most studies operated at room temperature it remains unclear whether the IL-associated boosting effect can be maintained at elevated temperature, which is of high relevance for practical applications in low temperature fuel cells. Herein, Fe-N-C catalysts were modified by introducing small amounts of hydrophobic ionic liquid, resulting in boosted electrocatalytic activity towards the alkaline oxygen reduction reaction at room temperature. It is demonstrated that the boosting effect can be maintained and even strengthened when increasing the electrolyte temperature up to 70℃. These findings show for the first time that the incorporation of ionic liquid is a suited method to obtain advanced noble metal-free electrocatalysts that can be applied at operating temperature condition.
