Cp_(2)TiCl_(2) as a Lewis acid precursor and nicotinic acid as a ligand have been used synergistically for the one-pot synthesis of 2-(N-substituted amino)-1,4-naphthoquinones.This method establishes a general strateg...Cp_(2)TiCl_(2) as a Lewis acid precursor and nicotinic acid as a ligand have been used synergistically for the one-pot synthesis of 2-(N-substituted amino)-1,4-naphthoquinones.This method establishes a general strategy for the functionalization and conversion of C-H bonds of 1,4-naphthoquinones into C-N bonds,providing an effective route to synthesize 2-(N-substituted amino)-1,4-naphthoquinone with high yield under mild conditions.Additionally,the synergistic catalytic mechanism was investigated by 1H NMR titration experiments and LC-MS analysis,with experimental results sufficiently and consistently supporting the proposed mechanism of the catalytic cycle.展开更多
Cyclopropylamine is synthesized with γ butyrolactone and isopropanol by five steps of ring opening esterification, cyclization, hydrolysis, acylation and Hofmann degradation. Cyclization and hydrolysis are key steps ...Cyclopropylamine is synthesized with γ butyrolactone and isopropanol by five steps of ring opening esterification, cyclization, hydrolysis, acylation and Hofmann degradation. Cyclization and hydrolysis are key steps in the process, and Phase Transfer Catalysis (PTC) is used in the two steps respectively. In the cyclization reaction, because solid liquid PTC, sodium hydroxide is applied instead of expensive sodium alcoholate, the reaction can be carried out in mild conditions. The optimum re action conditions are as follows: 0.03∶1∶1.5 mole ratio of BTEAC to ester to sodium hydroxide, reacting at 50 ℃ for 2 h with yield of 92%. Hydrolysis of isopropyl cyclopropanecarboxylate is accelerated by liquid liquid PTC, and the order of catalytic activity is BTEAC>BTMAC>CTMAB>TBAB. The results show that the new synthesis method is superior to those from literature and feasible for production with simple routes, mild reaction conditions, cheap materials and total yield of 52.6%.展开更多
The electrode is one of the main components in redox flow batteries(RFBs), as it provides the reactions sites for redox couples and can influence the cell performance through its effect on cell voltage losses associat...The electrode is one of the main components in redox flow batteries(RFBs), as it provides the reactions sites for redox couples and can influence the cell performance through its effect on cell voltage losses associated with activation overpotential, concentration overpotential and ohmic losses. Extensive research has thus been carried out on material selection, structural design and modification of electrodes as well as electrocatalysis for redox reactions. This review provides an historical overview of the screening and modification of electrode materials together with recent progress in novel electrode architectures, electrode modification and electrocatalysis methods. RFB systems such as iron/chromium, polysulfide/bromine and all vanadium batteries are discussed in detail.展开更多
p nitrophenol is synthesized using p nitrochlorobenzene and sodium hydroxide with phase transfer catalyst. Several reaction factors, such as catalyst type, the amounts of catalysts and sodium hydroxide, the concentrat...p nitrophenol is synthesized using p nitrochlorobenzene and sodium hydroxide with phase transfer catalyst. Several reaction factors, such as catalyst type, the amounts of catalysts and sodium hydroxide, the concentration of sodium hydroxide solution as well as reaction time, affect greatly the yield of p nitrophenol. The optimum reaction conditions are as follows: A 1 used as phase transfer catalyst whose consumption is 6% (mole fraction) of p nitrochlorobenzene; the molar ratio of sodium hydroxide to p nitrochlorobenzene is 3:1; the concentration of sodium hydroxide solution is 50% (mass fraction). Nitrobenzene, whose molar amount is 2.45 times as much as that of p nitrochlorobenzene; reaction time is 7 h at 140 ℃ under normal pressure. The final yield of p nitrophenol is 83.6%.展开更多
Lithium-sulfur(Li-S)batteries have great promise for next-generation energy storage devices due to the high theoretical specific capacity(1675 mAh g^(-1))of sulfur with chemical conversion for charge storage.However,t...Lithium-sulfur(Li-S)batteries have great promise for next-generation energy storage devices due to the high theoretical specific capacity(1675 mAh g^(-1))of sulfur with chemical conversion for charge storage.However,their practical use is hindered by the slow redox kinetics of sulfur and the“shuttle effect”arising from dissolved lithium polysulfides(LiPSs).In recent years,various carbon-based materials have served as sulfur hosts and catalysts for accelerating sulfur conversion redox kinetics and alleviating LiPS shuttling.However,they often suffer from irreversible passivation and structural changes that destroy their long-term performance.We consider the main problems limiting their stability,including excessive LiPS adsorption,passivation by insulating Li2S,and surface reconstruction,and clarify how these factors lead to capacity fade.We then outline effective strategies for achieving long-term sulfur catalysis,focusing on functional carbon,such as designing suitable carbon-supported catalyst interfaces,creating well-distributed active sites,adding cocatalysts to improve electron transfer,and using carbon-based protective layers to suppress unwanted side reactions.Using this information should enable the development of stable,high-activity catalysts capable of long-term operation under practical conditions in Li-S batteries.展开更多
The highly selective catalytic hydrogenation of halogenated nitroaromatics was achieved by employing Pd‑based catalysts that were co‑modified with organic and inorganic ligands.It was demonstrated that the catalysts c...The highly selective catalytic hydrogenation of halogenated nitroaromatics was achieved by employing Pd‑based catalysts that were co‑modified with organic and inorganic ligands.It was demonstrated that the catalysts contained Pd species in mixed valence states,with high valence Pd at the metal‑support interface and zero valence Pd at the metal surface.While the strong coordination of triphenylphosphine(PPh3)to Pd0 on the Pd surface prevents the adsorption of halogenated nitroaromatics and thus dehalogenation,the coordination of sodium metavanadate(NaVO3)to high‑valence Pd sites at the interface helps to activate H2 in a heterolytic pathway for the selective hydrogenation of nitro‑groups.The excellent catalytic performance of the interfacial active sites enables the selective hydrogenation of a wide range of halogenated nitroaromatics.展开更多
In this study,the catalysis function of Na_(2)CO_(3) to the structural properties of xylan char was well investigated with Na_(2)CO_(3) on,and the electrochemical performance of xylan char as an anode material for sod...In this study,the catalysis function of Na_(2)CO_(3) to the structural properties of xylan char was well investigated with Na_(2)CO_(3) on,and the electrochemical performance of xylan char as an anode material for sodium-ion batteries was tested.The characterization of X-ray microscopy and scanning electron microscopy demonstrated that the morphological structure of xylan char was altered due to the addition of Na_(2)CO_(3) catalyst.The increasement of the Na_(2)CO_(3)/xylan ratio resulted in a slenderization of the triangular prism shape of the char skeleton and a reduction in porosity.X-ray diffraction analysis revealed that Na_(2)CO_(3) promoted the growth of the(004)crystal plane of graphite during xylan pyrolysis,while inhibiting the formation of the(100/101)crystal planes.Raman spectroscopy analysis indicated that the presence of Na_(2)CO_(3)had changed the graphitization degree of xylan char.Electrochemical tests further showed that char prepared with a Na_(2)CO_(3)/xylan mass ratio of 1∶1 exhibited the highest sodium storage capacity.This study provides a pathway for the rational design carbon materials derived from xylan for future applications in energy storage devices.展开更多
CeO_(2) based semiconductor are widely used in solar-driven photothermal catalytic dry reforming of methane(DRM)reaction,but still suffer from low activity and low light utilization efficiency.This study developed gra...CeO_(2) based semiconductor are widely used in solar-driven photothermal catalytic dry reforming of methane(DRM)reaction,but still suffer from low activity and low light utilization efficiency.This study developed graphite-CeO_(2) interfaces to enhance solar-driven photothermal catalytic DRM.Compared with carbon nanotubes-modified CeO_(2)(CeO_(2)-CNT),graphite-modified CeO_(2)(CeO_(2)-GRA)constructed graphite-CeO_(2) interfaces with distortion in CeO_(2),leading to the formation abundant oxygen vacancies.These graphite-CeO_(2) interfaces with oxygen vacancies enhanced optical absorption and promoted the generation and separation of photogenerated carriers.The high endothermic capacity of graphite elevated the catalyst surface temperature from 592.1−691.3℃,boosting light-to-thermal conversion.The synergy between photogenerated carriers and localized heat enabled Ni/CeO_(2)-GRA to achieve a CO production rate of 9985.6 mmol/(g·h)(vs 7192.4 mmol/(g·h)for Ni/CeO_(2))and a light-to-fuel efficiency of 21.8%(vs 13.8%for Ni/CeO_(2)).This work provides insights for designing graphite-semiconductor interfaces to advance photothermal catalytic efficiency.展开更多
Fully utilizing renewable biomass energy is important for saving energy,reducing carbon emissions,and mitigating climate change.As the main hydrolysate of cellulose,a primary component of lignocellulose,glucose could ...Fully utilizing renewable biomass energy is important for saving energy,reducing carbon emissions,and mitigating climate change.As the main hydrolysate of cellulose,a primary component of lignocellulose,glucose could be employed as a starting material to prepare some other functional derivatives for improving the value of biomass resources.The isomerization of glucose to produce fructose is an important intermediate process during numerous high-value-added chemical preparations.Therefore,the development of efficient and selective catalysts for glucose isomerization is of great significance.Currently,glucose isomerase catalysts are limited by the harsh conditions required for microbial activity,which restricts further improvements in fructose yield.Additionally,heterogeneous Bronsted-base and Lewis-acid catalysts commonly employed in chemical isomerization methods often lead to the formation of undesirable by-products,resulting in reduced selectivity toward fructose.This study has demonstrated that lithium-loaded heterogeneous catalysts possess excellent isomerization capabilities under mild conditions.A highly efficient Li-C_(3)N_(4) catalyst was developed,achieving a fructose selectivity of 99.9% and a yield of 42.6% at 60℃ within 1.0 h-comparable to the performance of the enzymatic method.Characterization using X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD),proton nuclear magnetic resonance(^(1)H NMR),and inductively coupled plasma(ICP)analyses confirmed that lithium was stably incorporated into the g-C_(3)N_(4) framework through the formation of Li-N bonds.Further investigations using CO_(2) temperature-programmed desorption(CO_(2)-TPD),in situ Fourier-transform infrared spectroscopy(FT-IR)and 7Li magic angle spinning nuclear magnetic resonance(^(7)Li MAS NMR)indicated that the isomerization proceeded via a base-catalyzed mechanism.The Li species were found to interact with hydroxyl groups generated through hydrolysis and simultaneously coordinated with nitrogen atoms in the C_(3)N_(4) matrix,resulting in the formation of Li-N_(6)-H_(2)O active sites.These active sites facilitated the deprotonation of glucose to form an enolate intermediate,followed by a proton transfer step that generated fructose.This mechanism not only improved the efficiency of fructose production but also provided valuable insight into the catalytic role of lithium within the isomerization process.展开更多
The new technology of direct decomposition of H_(2)S into high value-added H_(2) and S,as an alternative to the Claus process in industry,is an ideal route that can not only deal with toxic and abundant H_(2)S waste g...The new technology of direct decomposition of H_(2)S into high value-added H_(2) and S,as an alternative to the Claus process in industry,is an ideal route that can not only deal with toxic and abundant H_(2)S waste gas but also recover clean energy H_(2),which has significant socio-economic and ecological advantages.However,the highly effective decomposition of H_(2)S at low temperatures is still a great challenge,because of the stringent thermodynamic equilibrium constraints(only 20% even at high temperature of 1010℃).Conventional microwave catalysts exhibit unsatisfactory performance at low temperatures(below 600℃).Herein,Mo_(2)C@CeO_(2) catalysts with a core-shell structure were successfully developed for robust microwave catalytic decomposition of H_(2)S at low temperatures.Two carbon precursors,para-phenylenediamine(Mo_(2)C-p)and meta-phenylenediamine(Mo_(2)C-m),were employed to tailor Mo_(2)C configurations.Remarkably,the H_(2)S conversion of Mo_(2)C-p@CeO_(2) catalyst at a low temperature of 550℃ is as high as 92.1%,which is much higher than the H_(2)S equilibrium conversion under the conventional thermal conditions(2.6% at 550℃).To our knowledge,this represents the most active catalyst for microwave catalytic decomposition of H_(2)S at low temperature of 550℃.Notably,Mo_(2)C-p demonstrated superior intrinsic activity(84%)compared to Mo_(2)C-m(6.4%),with XPS analysis revealing that its enhanced performance stems from a higher concentration of Mo_(2+)active sites.This work presents a substitute approach for the efficient utilization of H_(2)S waste gas and opens up a novel avenue for the rational design of microwave catalysts for microwave catalytic reaction at low-temperature.展开更多
《分子催化(中英文)》,Journal of Molecular Catalysis(China),是由中国科学院兰州化学物理研究所主办、中国科学院主管、中国科技出版传媒股份有限公司出版、国内外公开发行的学术性刊物.辟有学术论文、研究简报、研究快报及综合述评...《分子催化(中英文)》,Journal of Molecular Catalysis(China),是由中国科学院兰州化学物理研究所主办、中国科学院主管、中国科技出版传媒股份有限公司出版、国内外公开发行的学术性刊物.辟有学术论文、研究简报、研究快报及综合述评等栏目,主要报道有关分子催化方面最新进展与研究成果,内容侧重于配位催化、酶催化、光催化、催化过程中的立体化学问题、催化反应机理与动力学、催化剂表面态的研究及量子化学在催化学科中的应用等.本刊也刊载工业催化过程中的均相催化剂、固载化的均相催化剂、固载化的酶催化剂等活化、失活和再生,以及用于新催化过程的催化剂优选与表征等方面的内容.展开更多
By means of the Stopped—Flow Spectrophotometry,the kinetics of the reactions betweennickel（Ⅱ）and the ligand 5—bromopyridylazo diethylaminophenol（5-BrPADAP）and 3,5—dibromopyridylazo diethylaminophenol（3,5—2Br...By means of the Stopped—Flow Spectrophotometry,the kinetics of the reactions betweennickel（Ⅱ）and the ligand 5—bromopyridylazo diethylaminophenol（5-BrPADAP）and 3,5—dibromopyridylazo diethylaminophenol（3,5—2BrPADAP）have been investigated in themicellar solution of sodium dodecyl sulfate（SDS）.The reaction rate(compared with thatmeasured in aqueous solution for the same Ni<sup>2+</sup>concentration)was enhanced up to a factorof 400.Kinetic analysis indicates that the rate enhancement can be explained in terms of theconcentration effect of the micelles on the rcactants（i.e.partitioning coefficient effects）.Aquantitative expression for the rate enhancement is derived,using the psudo—phase modeland Berezin’s original micellar-catalysis coneepts.The influenccs of hydrophobic character-istics of ligands on the micellar-catalysis effect have been studied also.展开更多
The Journal of Molecular Catalysis(China)was first publishedin 1987 by the approval of the State Science and Technology Com-mission.It is an academic periodical circulated both domestically andinternationally.
This study explores the controllable synthesis of CuAlO_(2) using copper hydroxide and pseudo-boehmite powders as raw materials via a simple solid-phase ball milling method,along with its catalytic performance investi...This study explores the controllable synthesis of CuAlO_(2) using copper hydroxide and pseudo-boehmite powders as raw materials via a simple solid-phase ball milling method,along with its catalytic performance investigation in methanol steam reforming(MSR).Various catalysts were prepared under different conditions,such as calcination temperature,calcination atmosphere,and heating rate.Characterization techniques including BET,XRD,XPS,SEM and H2-TPR were employed to analyze the samples.The results revealed significant effects of calcination temperature on the phase compositions,specific surface area,reduction performance,and surface properties of the CA-T catalysts.Based on the findings,a synthesis route of CuAlO_(2) via the solid-phase method was proposed,highlighting the importance of high calcination temperature,nitrogen atmosphere,and low heating rate for CuAlO_(2) formation.Catalytic evaluation data demonstrated that CuAlO_(2) could catalyze MSR without pre-reduction,with the catalytic performance of CA-T catalysts being notably influenced by calcination temperature.Among the prepared catalysts,the CA-1100 catalyst exhibited the highest catalytic activity and stability.The findings of this study might be useful for the further study of the catalytic material for sustained release catalysis,including the synthesis of catalytic materials and the regulation of sustained release catalytic performance.展开更多
Ni/TiO_(2) catalyst is widely employed for photo-driven DRM reaction while the influence of crystal structure of TiO_(2) remains unclear.In this work,the rutile/anatase ratio in supports was successfully controlled by...Ni/TiO_(2) catalyst is widely employed for photo-driven DRM reaction while the influence of crystal structure of TiO_(2) remains unclear.In this work,the rutile/anatase ratio in supports was successfully controlled by varying the calcination temperature of anatase-TiO_(2).Structural characterizations revealed that a distinct TiO_(x) coating on the Ni nanoparticles(NPs)was evident for Ni/TiO_(2)-700 catalyst due to strong metal-support interaction.It is observed that the TiOx overlayer gradually disappeared as the ratio of rutile/anatase increased,thereby enhancing the exposure of Ni active sites.The exposed Ni sites enhanced visible light absorption and boosted the dissociation capability of CH4,which led to the much elevated catalytic activity for Ni/TiO_(2)-950 in which rutile dominated.Therefore,the catalytic activity of solar-driven DRM reaction was significantly influenced by the rutile/anatase ratio.Ni/TiO_(2)-950,characterized by a predominant rutile phase,exhibited the highest DRM reactivity,with remarkable H_(2) and CO production rates reaching as high as 87.4 and 220.2 mmol/(g·h),respectively.These rates were approximately 257 and 130 times higher,respectively,compared to those obtained on Ni/TiO_(2)-700 with anatase.This study suggests that the optimization of crystal structure of TiO_(2) support can effectively enhance the performance of photothermal DRM reaction.展开更多
Carbonylation reactions,crucial for carbonyl group incorporation,struggle with the inherent complexity of achieving selective mono-or double-carbonylation on single substrates,often due to competing reaction pathways....Carbonylation reactions,crucial for carbonyl group incorporation,struggle with the inherent complexity of achieving selective mono-or double-carbonylation on single substrates,often due to competing reaction pathways.Herein,our study introduces a strategy employing palladium amides,harnessing their unique reactivity control,to direct the selective carbonylation of amines for the targeted synthesis of urea and oxamide derivatives.The palladium amide structure was elucidated using single-crystal X-ray diffraction.Controlled experiments and cyclic voltammetry studies further elucidate that the oxidation of palladium amide or its insertion into a carbonyl group diverges into distinct pathways.By employing sodium percarbonate as an eco-friendly oxidant and base,we have successfully constructed a switchable carbonylation system co-catalyzed by palladium and iodide under room temperature.The utilizing strategy in this study not only facilitates effective control over reaction selectivity but also mitigates the risk of explosions,a critical safety concern in traditional carbonylation methods.展开更多
Research on two-dimensional(2D) materials has been explosively increasing in last seventeen years in varying subjects including condensed matter physics, electronic engineering, materials science, and chemistry since ...Research on two-dimensional(2D) materials has been explosively increasing in last seventeen years in varying subjects including condensed matter physics, electronic engineering, materials science, and chemistry since the mechanical exfoliation of graphene in 2004. Starting from graphene, 2D materials now have become a big family with numerous members and diverse categories. The unique structural features and physicochemical properties of 2D materials make them one class of the most appealing candidates for a wide range of potential applications. In particular, we have seen some major breakthroughs made in the field of 2D materials in last five years not only in developing novel synthetic methods and exploring new structures/properties but also in identifying innovative applications and pushing forward commercialisation. In this review, we provide a critical summary on the recent progress made in the field of 2D materials with a particular focus on last five years. After a brief backgroundintroduction, we first discuss the major synthetic methods for 2D materials, including the mechanical exfoliation, liquid exfoliation, vapor phase deposition, and wet-chemical synthesis as well as phase engineering of 2D materials belonging to the field of phase engineering of nanomaterials(PEN). We then introduce the superconducting/optical/magnetic properties and chirality of 2D materials along with newly emerging magic angle 2D superlattices. Following that, the promising applications of 2D materials in electronics, optoelectronics, catalysis, energy storage, solar cells, biomedicine, sensors, environments, etc. are described sequentially. Thereafter, we present the theoretic calculations and simulations of 2D materials. Finally, after concluding the current progress, we provide some personal discussions on the existing challenges and future outlooks in this rapidly developing field.展开更多
The absorbent composing of Bayer red mud and water was prepared and applied to removing SO2 from flue gas.Effects of the ratio of liquid to solid(L/S),the absorption temperature,the inlet SO2 concentration,the O2 conc...The absorbent composing of Bayer red mud and water was prepared and applied to removing SO2 from flue gas.Effects of the ratio of liquid to solid(L/S),the absorption temperature,the inlet SO2 concentration,the O2 concentration,SO4^2-and other different components of Bayer red mud on desulfurization were conducted.The mechanism of flue gas desulfurization was also established.The results indicated that L/S was the prominent factor,followed by the inlet SO2 concentration and the temperature was the least among them.The optimum condition was as follows:L/S,the temperature and the SO2 concentration were 20:1,25℃and 1000 mg/m^3,respectively,under the gas flow of 1.5 L/min.The desulfurization efficiency was not significantly influenced when O2 concentration was above 7%.The accumulation of SO4^2-inhibited the desulfurization efficiency.The alkali absorption and metal ions liquid catalytic oxidation were involved in the process,which accounted for 98.61%.展开更多
Improving the thermal decomposition performance of hexanitrohexaazaisowurtzitane(CL-20)by appropriate methods is helpful to promote the combustion performance of CL-20-based solid propellants.In this study,we synthesi...Improving the thermal decomposition performance of hexanitrohexaazaisowurtzitane(CL-20)by appropriate methods is helpful to promote the combustion performance of CL-20-based solid propellants.In this study,we synthesized a sandwich structure of CL-20 and nanoporous carbon scaffolds film(NCS)and emphatically studied the thermal decomposition performance of the composite structure.Thermogravimetric analysis and differential scanning calorimetry were used to measure the thermal decomposition process of the composite structure.The kinetic parameters of thermal decomposition were calculated by the thermal dynamic analysis software AKTS.These results showed that the thermal decomposition performance of the sandwich structure of CL-20 and NCS was better than CL-20.Among the tested samples,NCS with a pore size of 15 nm had the best catalytic activity for the thermal decomposition of CL-20.Moreover,the thermal decomposition curve of the composite structure at the heating rate of 1 K/min was deconvoluted by mathematical method to study the thermal decomposition process.And a possible catalytic mechanism was proposed.The excellent thermal decomposition performance is due to the sandwich structure enhances the interface reaction of CL-20 and NCS.This work may promote the extensive use of CL-20 in the field of solid rocket propellant.展开更多
基金2024 Special Talent Introduction Projects of Key R&D Program of Ningxia Hui Autonomous Region(2024BEH04049)the 2024 Guyuan City Innovation-Driven Achievement Transformation Project(2024BGTYF01-47)2025 Ningxia Natural Science Foundation Program(2025AAC030624).
文摘Cp_(2)TiCl_(2) as a Lewis acid precursor and nicotinic acid as a ligand have been used synergistically for the one-pot synthesis of 2-(N-substituted amino)-1,4-naphthoquinones.This method establishes a general strategy for the functionalization and conversion of C-H bonds of 1,4-naphthoquinones into C-N bonds,providing an effective route to synthesize 2-(N-substituted amino)-1,4-naphthoquinone with high yield under mild conditions.Additionally,the synergistic catalytic mechanism was investigated by 1H NMR titration experiments and LC-MS analysis,with experimental results sufficiently and consistently supporting the proposed mechanism of the catalytic cycle.
基金The Science and Research Foundation of Education Commission of Hunan Province
文摘Cyclopropylamine is synthesized with γ butyrolactone and isopropanol by five steps of ring opening esterification, cyclization, hydrolysis, acylation and Hofmann degradation. Cyclization and hydrolysis are key steps in the process, and Phase Transfer Catalysis (PTC) is used in the two steps respectively. In the cyclization reaction, because solid liquid PTC, sodium hydroxide is applied instead of expensive sodium alcoholate, the reaction can be carried out in mild conditions. The optimum re action conditions are as follows: 0.03∶1∶1.5 mole ratio of BTEAC to ester to sodium hydroxide, reacting at 50 ℃ for 2 h with yield of 92%. Hydrolysis of isopropyl cyclopropanecarboxylate is accelerated by liquid liquid PTC, and the order of catalytic activity is BTEAC>BTMAC>CTMAB>TBAB. The results show that the new synthesis method is superior to those from literature and feasible for production with simple routes, mild reaction conditions, cheap materials and total yield of 52.6%.
文摘The electrode is one of the main components in redox flow batteries(RFBs), as it provides the reactions sites for redox couples and can influence the cell performance through its effect on cell voltage losses associated with activation overpotential, concentration overpotential and ohmic losses. Extensive research has thus been carried out on material selection, structural design and modification of electrodes as well as electrocatalysis for redox reactions. This review provides an historical overview of the screening and modification of electrode materials together with recent progress in novel electrode architectures, electrode modification and electrocatalysis methods. RFB systems such as iron/chromium, polysulfide/bromine and all vanadium batteries are discussed in detail.
文摘p nitrophenol is synthesized using p nitrochlorobenzene and sodium hydroxide with phase transfer catalyst. Several reaction factors, such as catalyst type, the amounts of catalysts and sodium hydroxide, the concentration of sodium hydroxide solution as well as reaction time, affect greatly the yield of p nitrophenol. The optimum reaction conditions are as follows: A 1 used as phase transfer catalyst whose consumption is 6% (mole fraction) of p nitrochlorobenzene; the molar ratio of sodium hydroxide to p nitrochlorobenzene is 3:1; the concentration of sodium hydroxide solution is 50% (mass fraction). Nitrobenzene, whose molar amount is 2.45 times as much as that of p nitrochlorobenzene; reaction time is 7 h at 140 ℃ under normal pressure. The final yield of p nitrophenol is 83.6%.
文摘Lithium-sulfur(Li-S)batteries have great promise for next-generation energy storage devices due to the high theoretical specific capacity(1675 mAh g^(-1))of sulfur with chemical conversion for charge storage.However,their practical use is hindered by the slow redox kinetics of sulfur and the“shuttle effect”arising from dissolved lithium polysulfides(LiPSs).In recent years,various carbon-based materials have served as sulfur hosts and catalysts for accelerating sulfur conversion redox kinetics and alleviating LiPS shuttling.However,they often suffer from irreversible passivation and structural changes that destroy their long-term performance.We consider the main problems limiting their stability,including excessive LiPS adsorption,passivation by insulating Li2S,and surface reconstruction,and clarify how these factors lead to capacity fade.We then outline effective strategies for achieving long-term sulfur catalysis,focusing on functional carbon,such as designing suitable carbon-supported catalyst interfaces,creating well-distributed active sites,adding cocatalysts to improve electron transfer,and using carbon-based protective layers to suppress unwanted side reactions.Using this information should enable the development of stable,high-activity catalysts capable of long-term operation under practical conditions in Li-S batteries.
文摘The highly selective catalytic hydrogenation of halogenated nitroaromatics was achieved by employing Pd‑based catalysts that were co‑modified with organic and inorganic ligands.It was demonstrated that the catalysts contained Pd species in mixed valence states,with high valence Pd at the metal‑support interface and zero valence Pd at the metal surface.While the strong coordination of triphenylphosphine(PPh3)to Pd0 on the Pd surface prevents the adsorption of halogenated nitroaromatics and thus dehalogenation,the coordination of sodium metavanadate(NaVO3)to high‑valence Pd sites at the interface helps to activate H2 in a heterolytic pathway for the selective hydrogenation of nitro‑groups.The excellent catalytic performance of the interfacial active sites enables the selective hydrogenation of a wide range of halogenated nitroaromatics.
基金supported by the Foundation Project of Jihua Laboratory(X200191TL200).
文摘In this study,the catalysis function of Na_(2)CO_(3) to the structural properties of xylan char was well investigated with Na_(2)CO_(3) on,and the electrochemical performance of xylan char as an anode material for sodium-ion batteries was tested.The characterization of X-ray microscopy and scanning electron microscopy demonstrated that the morphological structure of xylan char was altered due to the addition of Na_(2)CO_(3) catalyst.The increasement of the Na_(2)CO_(3)/xylan ratio resulted in a slenderization of the triangular prism shape of the char skeleton and a reduction in porosity.X-ray diffraction analysis revealed that Na_(2)CO_(3) promoted the growth of the(004)crystal plane of graphite during xylan pyrolysis,while inhibiting the formation of the(100/101)crystal planes.Raman spectroscopy analysis indicated that the presence of Na_(2)CO_(3)had changed the graphitization degree of xylan char.Electrochemical tests further showed that char prepared with a Na_(2)CO_(3)/xylan mass ratio of 1∶1 exhibited the highest sodium storage capacity.This study provides a pathway for the rational design carbon materials derived from xylan for future applications in energy storage devices.
文摘CeO_(2) based semiconductor are widely used in solar-driven photothermal catalytic dry reforming of methane(DRM)reaction,but still suffer from low activity and low light utilization efficiency.This study developed graphite-CeO_(2) interfaces to enhance solar-driven photothermal catalytic DRM.Compared with carbon nanotubes-modified CeO_(2)(CeO_(2)-CNT),graphite-modified CeO_(2)(CeO_(2)-GRA)constructed graphite-CeO_(2) interfaces with distortion in CeO_(2),leading to the formation abundant oxygen vacancies.These graphite-CeO_(2) interfaces with oxygen vacancies enhanced optical absorption and promoted the generation and separation of photogenerated carriers.The high endothermic capacity of graphite elevated the catalyst surface temperature from 592.1−691.3℃,boosting light-to-thermal conversion.The synergy between photogenerated carriers and localized heat enabled Ni/CeO_(2)-GRA to achieve a CO production rate of 9985.6 mmol/(g·h)(vs 7192.4 mmol/(g·h)for Ni/CeO_(2))and a light-to-fuel efficiency of 21.8%(vs 13.8%for Ni/CeO_(2)).This work provides insights for designing graphite-semiconductor interfaces to advance photothermal catalytic efficiency.
基金supported by the National Natural Science Foundation of China(22278419)the Key Core Technology Research(Social Development)Foundation of Suzhou(2023ss06)the Suzhou National Joint Laboratory for Green and Low-carbon Wastewater Treatment and Resource Utilization Technology,Suzhou University of Science and Technology(SZLSDT202404).
文摘Fully utilizing renewable biomass energy is important for saving energy,reducing carbon emissions,and mitigating climate change.As the main hydrolysate of cellulose,a primary component of lignocellulose,glucose could be employed as a starting material to prepare some other functional derivatives for improving the value of biomass resources.The isomerization of glucose to produce fructose is an important intermediate process during numerous high-value-added chemical preparations.Therefore,the development of efficient and selective catalysts for glucose isomerization is of great significance.Currently,glucose isomerase catalysts are limited by the harsh conditions required for microbial activity,which restricts further improvements in fructose yield.Additionally,heterogeneous Bronsted-base and Lewis-acid catalysts commonly employed in chemical isomerization methods often lead to the formation of undesirable by-products,resulting in reduced selectivity toward fructose.This study has demonstrated that lithium-loaded heterogeneous catalysts possess excellent isomerization capabilities under mild conditions.A highly efficient Li-C_(3)N_(4) catalyst was developed,achieving a fructose selectivity of 99.9% and a yield of 42.6% at 60℃ within 1.0 h-comparable to the performance of the enzymatic method.Characterization using X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD),proton nuclear magnetic resonance(^(1)H NMR),and inductively coupled plasma(ICP)analyses confirmed that lithium was stably incorporated into the g-C_(3)N_(4) framework through the formation of Li-N bonds.Further investigations using CO_(2) temperature-programmed desorption(CO_(2)-TPD),in situ Fourier-transform infrared spectroscopy(FT-IR)and 7Li magic angle spinning nuclear magnetic resonance(^(7)Li MAS NMR)indicated that the isomerization proceeded via a base-catalyzed mechanism.The Li species were found to interact with hydroxyl groups generated through hydrolysis and simultaneously coordinated with nitrogen atoms in the C_(3)N_(4) matrix,resulting in the formation of Li-N_(6)-H_(2)O active sites.These active sites facilitated the deprotonation of glucose to form an enolate intermediate,followed by a proton transfer step that generated fructose.This mechanism not only improved the efficiency of fructose production but also provided valuable insight into the catalytic role of lithium within the isomerization process.
基金supported by the National Natural Science Foundation of China(22178295,21706225)Natural Science Foundation of Hunan Province(2025JJ50085)Hunan Collaborative Innovation Center of New Chemical Technologies for Environmental Benignity and Efficient Resource Utilization.
文摘The new technology of direct decomposition of H_(2)S into high value-added H_(2) and S,as an alternative to the Claus process in industry,is an ideal route that can not only deal with toxic and abundant H_(2)S waste gas but also recover clean energy H_(2),which has significant socio-economic and ecological advantages.However,the highly effective decomposition of H_(2)S at low temperatures is still a great challenge,because of the stringent thermodynamic equilibrium constraints(only 20% even at high temperature of 1010℃).Conventional microwave catalysts exhibit unsatisfactory performance at low temperatures(below 600℃).Herein,Mo_(2)C@CeO_(2) catalysts with a core-shell structure were successfully developed for robust microwave catalytic decomposition of H_(2)S at low temperatures.Two carbon precursors,para-phenylenediamine(Mo_(2)C-p)and meta-phenylenediamine(Mo_(2)C-m),were employed to tailor Mo_(2)C configurations.Remarkably,the H_(2)S conversion of Mo_(2)C-p@CeO_(2) catalyst at a low temperature of 550℃ is as high as 92.1%,which is much higher than the H_(2)S equilibrium conversion under the conventional thermal conditions(2.6% at 550℃).To our knowledge,this represents the most active catalyst for microwave catalytic decomposition of H_(2)S at low temperature of 550℃.Notably,Mo_(2)C-p demonstrated superior intrinsic activity(84%)compared to Mo_(2)C-m(6.4%),with XPS analysis revealing that its enhanced performance stems from a higher concentration of Mo_(2+)active sites.This work presents a substitute approach for the efficient utilization of H_(2)S waste gas and opens up a novel avenue for the rational design of microwave catalysts for microwave catalytic reaction at low-temperature.
文摘《分子催化(中英文)》,Journal of Molecular Catalysis(China),是由中国科学院兰州化学物理研究所主办、中国科学院主管、中国科技出版传媒股份有限公司出版、国内外公开发行的学术性刊物.辟有学术论文、研究简报、研究快报及综合述评等栏目,主要报道有关分子催化方面最新进展与研究成果,内容侧重于配位催化、酶催化、光催化、催化过程中的立体化学问题、催化反应机理与动力学、催化剂表面态的研究及量子化学在催化学科中的应用等.本刊也刊载工业催化过程中的均相催化剂、固载化的均相催化剂、固载化的酶催化剂等活化、失活和再生,以及用于新催化过程的催化剂优选与表征等方面的内容.
文摘By means of the Stopped—Flow Spectrophotometry,the kinetics of the reactions betweennickel（Ⅱ）and the ligand 5—bromopyridylazo diethylaminophenol（5-BrPADAP）and 3,5—dibromopyridylazo diethylaminophenol（3,5—2BrPADAP）have been investigated in themicellar solution of sodium dodecyl sulfate（SDS）.The reaction rate(compared with thatmeasured in aqueous solution for the same Ni<sup>2+</sup>concentration)was enhanced up to a factorof 400.Kinetic analysis indicates that the rate enhancement can be explained in terms of theconcentration effect of the micelles on the rcactants（i.e.partitioning coefficient effects）.Aquantitative expression for the rate enhancement is derived,using the psudo—phase modeland Berezin’s original micellar-catalysis coneepts.The influenccs of hydrophobic character-istics of ligands on the micellar-catalysis effect have been studied also.
文摘The Journal of Molecular Catalysis(China)was first publishedin 1987 by the approval of the State Science and Technology Com-mission.It is an academic periodical circulated both domestically andinternationally.
基金supported by the Scientific Research Foundation for High-level Talents of Anhui University of Science and Technology(2023yjrc51)the National Natural Science Foundation of China(22172184)+2 种基金the Foundation of State Key Laboratory of Coal Conversion(J24-25-603)the Fundamental Research Project of ICC-CAS(SCJC-DT-2023-01)Weiqiao-UCAS Special Projects on Low-Carbon Technology Development(GYY-DTFZ-2022-015)。
文摘This study explores the controllable synthesis of CuAlO_(2) using copper hydroxide and pseudo-boehmite powders as raw materials via a simple solid-phase ball milling method,along with its catalytic performance investigation in methanol steam reforming(MSR).Various catalysts were prepared under different conditions,such as calcination temperature,calcination atmosphere,and heating rate.Characterization techniques including BET,XRD,XPS,SEM and H2-TPR were employed to analyze the samples.The results revealed significant effects of calcination temperature on the phase compositions,specific surface area,reduction performance,and surface properties of the CA-T catalysts.Based on the findings,a synthesis route of CuAlO_(2) via the solid-phase method was proposed,highlighting the importance of high calcination temperature,nitrogen atmosphere,and low heating rate for CuAlO_(2) formation.Catalytic evaluation data demonstrated that CuAlO_(2) could catalyze MSR without pre-reduction,with the catalytic performance of CA-T catalysts being notably influenced by calcination temperature.Among the prepared catalysts,the CA-1100 catalyst exhibited the highest catalytic activity and stability.The findings of this study might be useful for the further study of the catalytic material for sustained release catalysis,including the synthesis of catalytic materials and the regulation of sustained release catalytic performance.
基金The project was supported by the National Key R&D Program of China(2021YFF0500702)Natural Science Foundation of Shanghai(22JC1404200)+3 种基金Program of Shanghai Academic/Technology Research Leader(20XD1404000)Natural Science Foundation of China(U22B20136,22293023)Science and Technology Major Project of Inner Mongolia(2021ZD0042)the Youth Innovation Promotion Association of CAS。
文摘Ni/TiO_(2) catalyst is widely employed for photo-driven DRM reaction while the influence of crystal structure of TiO_(2) remains unclear.In this work,the rutile/anatase ratio in supports was successfully controlled by varying the calcination temperature of anatase-TiO_(2).Structural characterizations revealed that a distinct TiO_(x) coating on the Ni nanoparticles(NPs)was evident for Ni/TiO_(2)-700 catalyst due to strong metal-support interaction.It is observed that the TiOx overlayer gradually disappeared as the ratio of rutile/anatase increased,thereby enhancing the exposure of Ni active sites.The exposed Ni sites enhanced visible light absorption and boosted the dissociation capability of CH4,which led to the much elevated catalytic activity for Ni/TiO_(2)-950 in which rutile dominated.Therefore,the catalytic activity of solar-driven DRM reaction was significantly influenced by the rutile/anatase ratio.Ni/TiO_(2)-950,characterized by a predominant rutile phase,exhibited the highest DRM reactivity,with remarkable H_(2) and CO production rates reaching as high as 87.4 and 220.2 mmol/(g·h),respectively.These rates were approximately 257 and 130 times higher,respectively,compared to those obtained on Ni/TiO_(2)-700 with anatase.This study suggests that the optimization of crystal structure of TiO_(2) support can effectively enhance the performance of photothermal DRM reaction.
基金The National Key Research and Development Program of Ministry of Science and Technology(No.2022YFA1504602)Natural Science Foundation of Jiangsu Province(No.BK20211094)National Natural Science Foundation of China(No.22302214,21972152,U22B20137).
文摘Carbonylation reactions,crucial for carbonyl group incorporation,struggle with the inherent complexity of achieving selective mono-or double-carbonylation on single substrates,often due to competing reaction pathways.Herein,our study introduces a strategy employing palladium amides,harnessing their unique reactivity control,to direct the selective carbonylation of amines for the targeted synthesis of urea and oxamide derivatives.The palladium amide structure was elucidated using single-crystal X-ray diffraction.Controlled experiments and cyclic voltammetry studies further elucidate that the oxidation of palladium amide or its insertion into a carbonyl group diverges into distinct pathways.By employing sodium percarbonate as an eco-friendly oxidant and base,we have successfully constructed a switchable carbonylation system co-catalyzed by palladium and iodide under room temperature.The utilizing strategy in this study not only facilitates effective control over reaction selectivity but also mitigates the risk of explosions,a critical safety concern in traditional carbonylation methods.
文摘Research on two-dimensional(2D) materials has been explosively increasing in last seventeen years in varying subjects including condensed matter physics, electronic engineering, materials science, and chemistry since the mechanical exfoliation of graphene in 2004. Starting from graphene, 2D materials now have become a big family with numerous members and diverse categories. The unique structural features and physicochemical properties of 2D materials make them one class of the most appealing candidates for a wide range of potential applications. In particular, we have seen some major breakthroughs made in the field of 2D materials in last five years not only in developing novel synthetic methods and exploring new structures/properties but also in identifying innovative applications and pushing forward commercialisation. In this review, we provide a critical summary on the recent progress made in the field of 2D materials with a particular focus on last five years. After a brief backgroundintroduction, we first discuss the major synthetic methods for 2D materials, including the mechanical exfoliation, liquid exfoliation, vapor phase deposition, and wet-chemical synthesis as well as phase engineering of 2D materials belonging to the field of phase engineering of nanomaterials(PEN). We then introduce the superconducting/optical/magnetic properties and chirality of 2D materials along with newly emerging magic angle 2D superlattices. Following that, the promising applications of 2D materials in electronics, optoelectronics, catalysis, energy storage, solar cells, biomedicine, sensors, environments, etc. are described sequentially. Thereafter, we present the theoretic calculations and simulations of 2D materials. Finally, after concluding the current progress, we provide some personal discussions on the existing challenges and future outlooks in this rapidly developing field.
基金Project(2017YFC0210500)supported by the National Key Technology R&D Program of ChinaProject(2017ACA092)supported by the Major Projects of Technical Innovation in Hubei Province,China
文摘The absorbent composing of Bayer red mud and water was prepared and applied to removing SO2 from flue gas.Effects of the ratio of liquid to solid(L/S),the absorption temperature,the inlet SO2 concentration,the O2 concentration,SO4^2-and other different components of Bayer red mud on desulfurization were conducted.The mechanism of flue gas desulfurization was also established.The results indicated that L/S was the prominent factor,followed by the inlet SO2 concentration and the temperature was the least among them.The optimum condition was as follows:L/S,the temperature and the SO2 concentration were 20:1,25℃and 1000 mg/m^3,respectively,under the gas flow of 1.5 L/min.The desulfurization efficiency was not significantly influenced when O2 concentration was above 7%.The accumulation of SO4^2-inhibited the desulfurization efficiency.The alkali absorption and metal ions liquid catalytic oxidation were involved in the process,which accounted for 98.61%.
基金supported by the National Natural Science Foundation of China(No:21975227)the Shanxi Province Graduate Student Innovation Project(No:2020SY403)。
文摘Improving the thermal decomposition performance of hexanitrohexaazaisowurtzitane(CL-20)by appropriate methods is helpful to promote the combustion performance of CL-20-based solid propellants.In this study,we synthesized a sandwich structure of CL-20 and nanoporous carbon scaffolds film(NCS)and emphatically studied the thermal decomposition performance of the composite structure.Thermogravimetric analysis and differential scanning calorimetry were used to measure the thermal decomposition process of the composite structure.The kinetic parameters of thermal decomposition were calculated by the thermal dynamic analysis software AKTS.These results showed that the thermal decomposition performance of the sandwich structure of CL-20 and NCS was better than CL-20.Among the tested samples,NCS with a pore size of 15 nm had the best catalytic activity for the thermal decomposition of CL-20.Moreover,the thermal decomposition curve of the composite structure at the heating rate of 1 K/min was deconvoluted by mathematical method to study the thermal decomposition process.And a possible catalytic mechanism was proposed.The excellent thermal decomposition performance is due to the sandwich structure enhances the interface reaction of CL-20 and NCS.This work may promote the extensive use of CL-20 in the field of solid rocket propellant.
