CO_(2) methanation has a potential in the large-scale utilization of carbon dioxide.It has also been considered to be useful for the renewable energy storage.The commercial pipeline for natural gas transportation can ...CO_(2) methanation has a potential in the large-scale utilization of carbon dioxide.It has also been considered to be useful for the renewable energy storage.The commercial pipeline for natural gas transportation can be directly applied for the methane product of CO_(2) methanation.The supported ruthenium(Ru)catalyst has been confirmed to be active and stable for CO_(2) methanation with its high ability in the dissociation of hydrogen and the strong binding of carbon monoxide.CO_(2) methanation over the supported Ru catalyst is structure sensitive.The size of the Ru catalyst and the support have significant effects on the activity and the mechanism.A significant challenge re-mained is the structural controllable preparation of the supported Ru catalyst toward a sufficiently high low-temperature activity.In this review,the recent progresses in the investigations of the supported Ru catalysts for CO_(2) methanation are summarized.The challenges and the future devel-opments are also discussed.展开更多
Light olefins are important platform feedstocks in the petrochemical industry,and the ongoing global economic development has driven sustained growth in demand for these compounds.The dehydrogenation of alkanes,derive...Light olefins are important platform feedstocks in the petrochemical industry,and the ongoing global economic development has driven sustained growth in demand for these compounds.The dehydrogenation of alkanes,derived from shale gas,serves as an alternative olefins production route.Concurrently,the target of realizing carbon neutrality promotes the comprehensive utilization of greenhouse gas.The integrated process of light alkanes dehydrogenation and carbon dioxide reduction(CO_(2)-ODH)can produce light olefins and realize resource utilization of CO_(2),which has gained wide popularity.With the introduction of CO_(2),coke deposition and metal reduction encountered in alkanes dehydrogenation reactions can be effectively suppressed.CO_(2)-assisted alkanes dehydrogenation can also reduce the risk of potential explosion hazard associated with O_(2)-oxidative dehydrogenation reactions.Recent investigations into various metal-based catalysts including mono-and bi-metallic alloys and oxides have displayed promising performances due to their unique properties.This paper provides the comprehensive review and critical analysis of advancements in the CO_(2)-assisted oxidative dehydrogenation of light alkanes(C2-C4)on metal-based catalysts developed in recent years.Moreover,it offers a comparative summary of the structural properties,catalytic activities,and reaction mechanisms over various active sites,providing valuable insights for the future design of dehydrogenation catalysts.展开更多
Noble metal-based-bimetallic catalysts have been highly investigated and applied in wide applications including biomass transformation via regioselective C−O hydrogenolysis while further modification especially with n...Noble metal-based-bimetallic catalysts have been highly investigated and applied in wide applications including biomass transformation via regioselective C−O hydrogenolysis while further modification especially with noble metal is highly promising yet still under investigation.Herein,Ru was found as an effective modifier among the screened noble metals(Ru,Pt,Rh,Pd,Au,and Ag)for Ir-Fe/BN(Ir=5 wt%,Fe/Ir=0.25)catalyst in terminal C−O hydrogenolysis of 1,2-butanediol(1,2-BuD)to 2-butanol(2-BuOH).Only trace amount of Ru(up to 0.5 wt%)was effective in terms of high 2-BuOH selectivity(>60%)and activity(about twice).Larger amount of Ru species(3 wt%)highly enhanced the activity but gave low selectivity to 2-BuOH with by-products of terminal C−C bond scission.Optimized catalyst(Ru(0.5)-Ir-Fe/BN)was reusable at least 4 times and gave moderate 2-BuOH yield(47%)in hydrogenolysis of 1,2-BuD.The promoting effect of Ru addition(0.5 wt%)to Ir-Fe/BN on hydrogenolysis of various alcohols was also confirmed.Combining catalytic tests with various characterizations,the promotion mechanism of Ru species in trimetallic catalysts was clarified.The Ru species in Ru(0.5)-Ir-Fe/BN form alloy with Ir and are enriched at the interface with BN surface,and direct interaction between Ru and Fe was not necessary in Ru-Ir-Fe alloy.The interface of Ir and Fe on the surface of Ir-Fe alloy may work as active sites for 1,2-diols to secondary alcohols via direct C−O hydrogenolysis,in which Ru-modified Ir activates H_(2) to form hydride-like species.The activity of Ru species in C−C bond cleavage was highly suppressed due to the direct interaction with Ir species and less exposed to substrate.Larger loading amount of Ru species(3 wt%)led to the formation Ru-rich trimetallic alloy,which further works as active sites for C−C bond scission.展开更多
Layered double Mg-Fe-CO3 hydroxide (Mg-Fe-LDH) with a mole ratio of Mg to Fe of 3 was synthesized by coprecipitation method and calcined product Mg-Fe-CLDH was obtained by heating Mg-Fe-LDH at 500 ℃ for 6 h. The as...Layered double Mg-Fe-CO3 hydroxide (Mg-Fe-LDH) with a mole ratio of Mg to Fe of 3 was synthesized by coprecipitation method and calcined product Mg-Fe-CLDH was obtained by heating Mg-Fe-LDH at 500 ℃ for 6 h. The as prepared Mg-Fe-LDH and calcined Mg-Fe-CLDH were used for removal of glutamic acid (Glu) from aqueous solution, respectively. Batch studies were carried out to address various experimental parameters such as contact time, pH, initial glutamic acid (Glu) concentration, co-existing anions and temperature. Glu was removed effectively (99.9%) under the optimized experimental conditions with Mg-Fe-CLDH. The adsorption kinetics follows the Ho’s pseudo second-order model. Isotherms for adsorption with Mg-Fe-CLDH at different solution temperatures were well described using the Langmuir model with a good correlation coefficient. The intraparticle diffusion model fitted the data well, which suggests that the intraparticle diffusion is not only the rate-limiting step.展开更多
A formula was proposed to calculate the distribution of metal ions quantitatively in chemical reaction system forming hydroxide where precipitation and complex are formed together. The effects of some factors on forma...A formula was proposed to calculate the distribution of metal ions quantitatively in chemical reaction system forming hydroxide where precipitation and complex are formed together. The effects of some factors on formation of precipitation and complex were investigated, and the corresponding precipitation rates of zinc, iron (III), aluminum, copper and magnesium were calculated. As a result, it shows that the proposed formula is reliable. By the proposed formula, the existence state of metal ions in hydroxides reaction system with any metal ions can be well described and the effects of some factors on the distribution of metal ions were determined.展开更多
The catalytic effects of the organic compounds of iron,tin and manganese on the degradation of low density polyethylene (LDPE) at compost temperature are discussed.A series of samples were aged in a simulating compost...The catalytic effects of the organic compounds of iron,tin and manganese on the degradation of low density polyethylene (LDPE) at compost temperature are discussed.A series of samples were aged in a simulating compost environment.The mechanical properties,viscosity average molecular weight (M η) of PE and hydroperoxide (POOH) concentration in the samples were measured.FT IR and DSC were also applied to characterize some samples.It was shown that the above mentioned metallic organic compounds can catalyze the degradation of LDPE efficiently.After 2 months aging,all samples with catalysts became fragile and the M η of the material decreased dramatically.Furthermore,the concentration of carbonyl and the degree of crystallinity of the material increased with the aging time.展开更多
The assembly of layered double hydroxides (LDHs) and multi-walled carbon nanotubes (MWCNTs) nanohybrids was prepared as MWCNTs/LDHs by co-precipitation. The synthesized nanoparticles were characterized by us...The assembly of layered double hydroxides (LDHs) and multi-walled carbon nanotubes (MWCNTs) nanohybrids was prepared as MWCNTs/LDHs by co-precipitation. The synthesized nanoparticles were characterized by using XRD, FT-IR, SEM/EDX, TGA and BET. XRD and SEM studies proved that MWCNTs phases did not enter into the interlayers of LDHs, they dispersed over the LDHs surface homogeneously. BET results showed that MWCNTs/LDHs possessed hierarchically porous nanostructure with large surface area (124.974 m^2/g) and great pore volume (0.604 cm^3/g). Batch experiments were conducted to study the adsorption efficiency of Congo red (CR). It was worthy to note that MWCNTs/LDHs exhibited excellent adsorption performance with the maximum CR adsorption capacity of 595.8 mg/g in weak acidic environment. The adsorption kinetics and isotherm parameters can be well described by the pseudo-second-order and the Langmuir isotherm models, respectively. The thermodynamic studies indicated that the adsorption process was spontaneous and endothermic.展开更多
To further enhance the corrosion resistance of the porous micro-arc oxidation(MAO) ceramic layers on AZ31 magnesium alloy, superhydrophobic Mg-Al layered double hydroxide(LDH) coating was fabricated on MAO-coated AZ31...To further enhance the corrosion resistance of the porous micro-arc oxidation(MAO) ceramic layers on AZ31 magnesium alloy, superhydrophobic Mg-Al layered double hydroxide(LDH) coating was fabricated on MAO-coated AZ31 alloy by using in-situ growth method followed by surface modification with stearic acid. The characteristics of different coatings were investigated by XRD, SEM and EDS. The effect of the hydrothermal treatment time on the formation of the LDH coatings was studied. The results demonstrated that the micro-pores and cracks of MAO coating were gradually sealed via in-situ growing LDH with prolonging hydrothermal treating time. Electrochemical measurement displayed that the lowest corrosion current density, the most positive corrosion potential and the highest impedance modulus were observed for superhydrophobic LDH/MAO coating compared with those of MAO coating and LDH/MAO coating. Immersion experiment proved that the superhydrophobic LDH/MAO coating with the active anti-corrosion capability significantly enhanced the long-term corrosion protection for MAO coated alloy.展开更多
Hydrogen is a promising sustainable energy to replace fossil fuels owning to its high specific energy and environmental friendliness.Alkaline water electrolysis has been considered as one of the most prospective techn...Hydrogen is a promising sustainable energy to replace fossil fuels owning to its high specific energy and environmental friendliness.Alkaline water electrolysis has been considered as one of the most prospective technologies for large scale hydrogen production.To boost the sluggish kinetics of hydrogen evolution reaction(HER)in alkaline media,abundant materials have been designed and fabricated.Herein,we summarize the key achievements in the development of layered transition-metal hydroxides[TM(OH)x]for efficient alkaline HER.Based on the structure of TM(OH)x,the mechanism of synergistic effect between TM(OH)x and HER active materials is illuminated firstly.Then,recent progress of TM(OH)x-based HER catalysts to optimize the synergistic effect are categorized as TM(OH)x and active materials,including species,structure,morphology and interaction relationship.Furthermore,TM(OH)x-based overall water splitting electrocatalysts and electrodes are summarized in the design principles for high activity and stability.Finally,some of key challenges for further developments and applications of hydrogen production are proposed.展开更多
Bimetallic nanostructures have attracted great interest as efficient catalyst to enhance activity,selectivity and stability in catalytical conversion.Herein,we report a facile one‐pot carbothermal route to in‐situ c...Bimetallic nanostructures have attracted great interest as efficient catalyst to enhance activity,selectivity and stability in catalytical conversion.Herein,we report a facile one‐pot carbothermal route to in‐situ controllable synthesize heterogeneous bimetallic Ni3Fe NPs@C nanocatalyst.The X‐ray diffraction,transmission electron microscopy,X‐ray photoelectron spectroscopy and N2 adsorption‐description results reveal that the Ni3Fe alloy nanoparticles are evenly embedded in carbon matrix.The as‐prepared Ni3Fe NPs@C catalyst shows excellent selective hydrogenation catalytic performance toward the conversion of levulinic acid(LA)toγ‐valerolactone(GVL)via both direct hydrogenation(DH)and transfer hydrogenation(TH).In DH of LA,the bimetallic catalyst achieved a 93.8%LA conversion efficiency with a 95.5%GVL selectivity and 38.2 mmol g–1 h–1 GVL productivity(under 130°C,2MPa H2 within 2 h),which are 6 and 40 times in comparison with monometallic Ni NPs@C and Fe NPs@C catalysts,respectively.In addition,the identical catalyst displayed a full conversion of LA with almost 100%GVL selectivity and 167.1 mmol g–1 h–1 GVL productivity at 180°C within 0.5 h in TH of LA.Under optimal reaction conditions,the DH and TH catalytic performance of 500‐Ni3Fe NPs@C(3:1)catalyst for converting LA to GVL is comparable to the state‐of‐the‐art noble‐based catalysts.The demonstrated capability of bimetallic catalyst design approach to introduce dual‐catalytic functionality for DH and TH reactions could be adoptable for other catalysis processes.展开更多
Splitting water or reducing CO_(2) via semiconductor photocatalysis to produce H2 or hydrocarbon fuels through the direct utilization of solar energy is a promising approach to mitigating the current fossil fuel energ...Splitting water or reducing CO_(2) via semiconductor photocatalysis to produce H2 or hydrocarbon fuels through the direct utilization of solar energy is a promising approach to mitigating the current fossil fuel energy crisis and environmental challenges.It enables not only the realization of clean,renewable,and high-heating-value solar fuels,but also the reduction of CO_(2) emissions.Layered double hydroxides(LDHs)are a type of two-dimensional anionic clay with a brucite-like structure,and are characterized by a unique,delaminable,multidimensional,layered structure;tunable intralayer metal cations;and exchangeable interlayer guest anions.Therefore,it has been widely investigated in the fields of CO_(2) reduction,photoelectrocatalytic water oxidation,and water photolysis to produce H2.However,the low carrier mobility and poor quantum efficiency of pure LDH limit its application.An increasing number of scholars are exploring methods to obtain LDH-based photocatalysts with high energy conversion efficiency,such as assembling photoactive components into LDH laminates,designing multidimensional structures,or coupling different types of semiconductors to construct heterojunctions.This review first summarizes the main characteristics of LDH,i.e.,metal-cation tunability,intercalated guest-anion substitutability,thermal decomposability,memory effect,multidimensionality,and delaminability.Second,LDHs,LDH-based composites(metal sulfide-LDH composites,metal oxide-LDH composites,graphite phase carbon nitride-LDH composites),ternary LDH-based composites,and mixed-metal oxides for splitting water to produce H_(2) are reviewed.Third,graphite phase carbon nitride-LDH composites,MgAl-LDH composites,CuZn-LDH composites,and other semiconductor-LDH composites for CO_(2) reduction are introduced.Although the field of LDH-based photocatalysts has advanced considerably,the photocatalytic mechanism of LDHs has not been thoroughly elucidated;moreover,the photocatalytic active sites,the synergy between different components,and the interfacial reaction mechanism of LDH-based photocatalysts require further investigation.Therefore,LDH composite materials for photocatalysis could be developed through structural regulation and function-oriented design to investigate the effects of different components and interface reactions,the influence of photogenerated carriers,and the impact of material composition on the physical and chemical properties of the LDH-based photocatalyst.展开更多
Photocatalytic hydrogen production based on semiconductor photocatalysts has been considered as one of the most promising strategies to resolve the global energy shortage.Graphitic carbon nitride(g‐C3N4)has been a st...Photocatalytic hydrogen production based on semiconductor photocatalysts has been considered as one of the most promising strategies to resolve the global energy shortage.Graphitic carbon nitride(g‐C3N4)has been a star visible‐light photocatalyst in this field due to its various advantages.However,pristine g‐C3N4usually exhibits limited activity.Herein,to enhance the performance of g‐C3N4,alkali metal ion(Li+,Na+,or K+)‐doped g‐C3N4are prepared via facile high‐temperature treatment.The prepared samples are characterized and analyzed using the technique of XRD,ICP‐AES,SEM,UV‐vis DRS,BET,XPS,PL,TRPL,photoelectrochemical measurements,photocatalytic tests,etc.The resultant doped photocatalysts show enhanced visible‐light photocatalytic activities for hydrogen production,benefiting from the increased specific surface areas(which provide more active sites),decreased band gaps for extended visible‐light absorption,and improved electronic structures for efficient charge transfer.In particular,because of the optimal tuning of both microstructure and electronic structure,the Na‐doped g‐C3N4shows the most effective utilization of photogenerated electrons during the water reduction process.As a result,the highest photocatalytic performance is achieved over the Na‐doped g‐C3N4photocatalyst(18.7?mol/h),3.7times that of pristine g‐C3N4(5.0?mol/h).This work gives a systematic study for the understanding of doping effect of alkali metals in semiconductor photocatalysis.展开更多
To extract selenium(Ⅵ)from the highly caustic leachate of copper anode slime,the Ca-Al-Cl layered double hydroxides(Ca-Al-Cl-LDHs)with a formula of Ca2 Al(OH)6 Cl·2 H2 O by three co-precipitation methods were sy...To extract selenium(Ⅵ)from the highly caustic leachate of copper anode slime,the Ca-Al-Cl layered double hydroxides(Ca-Al-Cl-LDHs)with a formula of Ca2 Al(OH)6 Cl·2 H2 O by three co-precipitation methods were synthesized.A plate-like morphology and hexagonal crystal structure with typical mineral phases and functional groups were identified by the FESEM,XRD,FTIR,BET and XPS analysis.The forward feeding sample exhibits the best adsorption capacity of Se(Ⅵ).The factor experiments then reveal a favorable adsorption process with low temperature,low NaOH concentration and high adsorbent dosage.Furthermore,the adsorption kinetics and isotherm parameters can be well described by the Langmuir isotherm and the pseudo-second-order models,respectively.Accordingly,the maximum adsorption amount of Se(Ⅵ)onto Ca-Al-Cl-LDHs reaches188.6 mg/g at 50 ℃.展开更多
Metal-organic-framework (MOF)-based materials with novel physicochemical properties have emerged as promising catalysts for various hydrogenation reactions. In addition to metal clusters and multifunctional organic...Metal-organic-framework (MOF)-based materials with novel physicochemical properties have emerged as promising catalysts for various hydrogenation reactions. In addition to metal clusters and multifunctional organic ligands, MOF-based catalysts can incorporate other functional species, and thus provide various active sites for hydrogenation processes. The structural properties of the catalysts play significant roles in enhancing the interactions among the reactants, products, and catalytic sites, which can be rationally designed. Because of the synergistic effects between the ac-tive sites and the structural properties, MOF-based catalysts can achieve higher activities and selec- tivities in hydrogenation reactions than can be obtained using traditional heterogeneous catalysts. This review provides an overview of recent developments in MOF-based catalysts in the hydro-genation of alkenes, alkynes, nitroarenes, cinnamaldehyde, furfural, benzene, and other compounds. Strategies for improving the catalytic performances of MOF-based catalysts are discussed as well as the different active sites and structural properties of the catalysts.展开更多
Photocatalytic hydrogen(H2)evolution is a promising approach for future sustainable energy utilization.However,it is still a great challenge to develop efficient and stable metal‐free photocatalysts with broadband so...Photocatalytic hydrogen(H2)evolution is a promising approach for future sustainable energy utilization.However,it is still a great challenge to develop efficient and stable metal‐free photocatalysts with broadband solar absorption in the visible region for H2 production.Metal‐free graphene quantum dot(GQD)is an emerging candidate for this purpose because of its good water‐solubility and tunable band gap.On the other hand,metal phosphides(Ni2P,Co2P,etc)have been demonstrated as novel noble‐metal‐free cocatalysts for water splitting,which can efficiently separate electron‐hole pairs and enhance the photocatalytic activities.Herein,we report for the first time on the use of OH‐functionalized GQDs(OH‐GQDs)photosensitizer coupled with Ni2P nanoparticles for photocatalytic H2 production withλ>420 nm light.The H2 production rate is^94 times higher than that of bare OH‐GQDs,which is even comparable to that of OH‐GQDs with 1.0 wt%Pt cocatalyst.This enhancement is probably due to the semiconductor‐cocatalyst interface interaction between Ni2P and OH‐GQDs to facilitate efficient charge transfer process.展开更多
Exploring highly efficient electrochemical water splitting catalysts has recently attracted extensive research interest from both fundamental researches and practical applications.Transition metal‐based layered doubl...Exploring highly efficient electrochemical water splitting catalysts has recently attracted extensive research interest from both fundamental researches and practical applications.Transition metal‐based layered double hydroxides(LDHs)have been proved to be one of the most efficient materials for oxygen evolution reaction(OER),however,still suffered from low conductivity and sluggish kinetics for hydrogen evolution reaction(HER),which largely inhibited the overall water splitting efficiency.To address this dilemma,enormous approaches including doping regulation,intercalation tuning and defect engineering are therefore rationally designed and developed.Herein,we focus on the recent exciting progress of LDHs hybridization with other two‐dimensional(2D)materials for water splitting reactions,not barely for enhancing OER efficiency but also for boosting HER activity.Particularly,the structural features,morphologies,charge transfer and synergistic effects for the heterostructure/heterointerface that influence the electrocatalytic performance are discussed in details.The hybrid 2D building blocks not only serve as additional conductivity and structural supported but also promote electron transfer at the interfaces and further enhance the electrocatalytic performance.The construction and application of the nanohybrid materials will guide a new direction in developing multifunctional materials based on LDHs,which will contribute to energy conversion and storage.展开更多
TiO2‐supported Pd‐Sb bimetallic catalysts were prepared and evaluated for the direct synthesis of H2O2 at ambient pressure.The addition of Sb to Pd significantly enhanced catalytic performance,and a Pd50Sb catalyst ...TiO2‐supported Pd‐Sb bimetallic catalysts were prepared and evaluated for the direct synthesis of H2O2 at ambient pressure.The addition of Sb to Pd significantly enhanced catalytic performance,and a Pd50Sb catalyst showed the greatest selectivity of up to 73%.Sb promoted the dispersion of Pd on TiO2,as evidenced by transmission electron microscopy and X‐ray diffraction.X‐ray photoelectron spectroscopy indicated that the oxidation of Pd was suppressed by Sb.In addition,Sb2O3 layers were formed and partially wrapped the surfaces of Pd catalysts,thus suppressing the activation of H2 and subsequent hydrogenation of H2O2.In situ diffuse reflection infrared Fourier transform spectroscopy for CO adsorption suggested that Sb homogenously located on the surface of Pd‐Sb catalysts and isolated contiguous Pd sites,resulting in the rise of the ratio of Pd monomer sites that are favorable for H2O2 formation.As a result,the Sb modified Pd surfaces significantly enhanced the non‐dissociative activation of O2 and H2O2 selectivity.展开更多
文摘CO_(2) methanation has a potential in the large-scale utilization of carbon dioxide.It has also been considered to be useful for the renewable energy storage.The commercial pipeline for natural gas transportation can be directly applied for the methane product of CO_(2) methanation.The supported ruthenium(Ru)catalyst has been confirmed to be active and stable for CO_(2) methanation with its high ability in the dissociation of hydrogen and the strong binding of carbon monoxide.CO_(2) methanation over the supported Ru catalyst is structure sensitive.The size of the Ru catalyst and the support have significant effects on the activity and the mechanism.A significant challenge re-mained is the structural controllable preparation of the supported Ru catalyst toward a sufficiently high low-temperature activity.In this review,the recent progresses in the investigations of the supported Ru catalysts for CO_(2) methanation are summarized.The challenges and the future devel-opments are also discussed.
文摘Light olefins are important platform feedstocks in the petrochemical industry,and the ongoing global economic development has driven sustained growth in demand for these compounds.The dehydrogenation of alkanes,derived from shale gas,serves as an alternative olefins production route.Concurrently,the target of realizing carbon neutrality promotes the comprehensive utilization of greenhouse gas.The integrated process of light alkanes dehydrogenation and carbon dioxide reduction(CO_(2)-ODH)can produce light olefins and realize resource utilization of CO_(2),which has gained wide popularity.With the introduction of CO_(2),coke deposition and metal reduction encountered in alkanes dehydrogenation reactions can be effectively suppressed.CO_(2)-assisted alkanes dehydrogenation can also reduce the risk of potential explosion hazard associated with O_(2)-oxidative dehydrogenation reactions.Recent investigations into various metal-based catalysts including mono-and bi-metallic alloys and oxides have displayed promising performances due to their unique properties.This paper provides the comprehensive review and critical analysis of advancements in the CO_(2)-assisted oxidative dehydrogenation of light alkanes(C2-C4)on metal-based catalysts developed in recent years.Moreover,it offers a comparative summary of the structural properties,catalytic activities,and reaction mechanisms over various active sites,providing valuable insights for the future design of dehydrogenation catalysts.
文摘Noble metal-based-bimetallic catalysts have been highly investigated and applied in wide applications including biomass transformation via regioselective C−O hydrogenolysis while further modification especially with noble metal is highly promising yet still under investigation.Herein,Ru was found as an effective modifier among the screened noble metals(Ru,Pt,Rh,Pd,Au,and Ag)for Ir-Fe/BN(Ir=5 wt%,Fe/Ir=0.25)catalyst in terminal C−O hydrogenolysis of 1,2-butanediol(1,2-BuD)to 2-butanol(2-BuOH).Only trace amount of Ru(up to 0.5 wt%)was effective in terms of high 2-BuOH selectivity(>60%)and activity(about twice).Larger amount of Ru species(3 wt%)highly enhanced the activity but gave low selectivity to 2-BuOH with by-products of terminal C−C bond scission.Optimized catalyst(Ru(0.5)-Ir-Fe/BN)was reusable at least 4 times and gave moderate 2-BuOH yield(47%)in hydrogenolysis of 1,2-BuD.The promoting effect of Ru addition(0.5 wt%)to Ir-Fe/BN on hydrogenolysis of various alcohols was also confirmed.Combining catalytic tests with various characterizations,the promotion mechanism of Ru species in trimetallic catalysts was clarified.The Ru species in Ru(0.5)-Ir-Fe/BN form alloy with Ir and are enriched at the interface with BN surface,and direct interaction between Ru and Fe was not necessary in Ru-Ir-Fe alloy.The interface of Ir and Fe on the surface of Ir-Fe alloy may work as active sites for 1,2-diols to secondary alcohols via direct C−O hydrogenolysis,in which Ru-modified Ir activates H_(2) to form hydride-like species.The activity of Ru species in C−C bond cleavage was highly suppressed due to the direct interaction with Ir species and less exposed to substrate.Larger loading amount of Ru species(3 wt%)led to the formation Ru-rich trimetallic alloy,which further works as active sites for C−C bond scission.
基金Project(21176263)supported by the National Natural Science Foundation of China
文摘Layered double Mg-Fe-CO3 hydroxide (Mg-Fe-LDH) with a mole ratio of Mg to Fe of 3 was synthesized by coprecipitation method and calcined product Mg-Fe-CLDH was obtained by heating Mg-Fe-LDH at 500 ℃ for 6 h. The as prepared Mg-Fe-LDH and calcined Mg-Fe-CLDH were used for removal of glutamic acid (Glu) from aqueous solution, respectively. Batch studies were carried out to address various experimental parameters such as contact time, pH, initial glutamic acid (Glu) concentration, co-existing anions and temperature. Glu was removed effectively (99.9%) under the optimized experimental conditions with Mg-Fe-CLDH. The adsorption kinetics follows the Ho’s pseudo second-order model. Isotherms for adsorption with Mg-Fe-CLDH at different solution temperatures were well described using the Langmuir model with a good correlation coefficient. The intraparticle diffusion model fitted the data well, which suggests that the intraparticle diffusion is not only the rate-limiting step.
基金Project (51304047) supported by the National Natural Science Foundation of ChinaProject (20131037) supported by Science and Technology Foundation of Liaoning Province,China
文摘A formula was proposed to calculate the distribution of metal ions quantitatively in chemical reaction system forming hydroxide where precipitation and complex are formed together. The effects of some factors on formation of precipitation and complex were investigated, and the corresponding precipitation rates of zinc, iron (III), aluminum, copper and magnesium were calculated. As a result, it shows that the proposed formula is reliable. By the proposed formula, the existence state of metal ions in hydroxides reaction system with any metal ions can be well described and the effects of some factors on the distribution of metal ions were determined.
文摘The catalytic effects of the organic compounds of iron,tin and manganese on the degradation of low density polyethylene (LDPE) at compost temperature are discussed.A series of samples were aged in a simulating compost environment.The mechanical properties,viscosity average molecular weight (M η) of PE and hydroperoxide (POOH) concentration in the samples were measured.FT IR and DSC were also applied to characterize some samples.It was shown that the above mentioned metallic organic compounds can catalyze the degradation of LDPE efficiently.After 2 months aging,all samples with catalysts became fragile and the M η of the material decreased dramatically.Furthermore,the concentration of carbonyl and the degree of crystallinity of the material increased with the aging time.
基金Project(21476269)supported by the National Natural Science Foundation of ChinaProject(14JJ2014)supported by Natural Science Foundation of Hunan Province,China
文摘The assembly of layered double hydroxides (LDHs) and multi-walled carbon nanotubes (MWCNTs) nanohybrids was prepared as MWCNTs/LDHs by co-precipitation. The synthesized nanoparticles were characterized by using XRD, FT-IR, SEM/EDX, TGA and BET. XRD and SEM studies proved that MWCNTs phases did not enter into the interlayers of LDHs, they dispersed over the LDHs surface homogeneously. BET results showed that MWCNTs/LDHs possessed hierarchically porous nanostructure with large surface area (124.974 m^2/g) and great pore volume (0.604 cm^3/g). Batch experiments were conducted to study the adsorption efficiency of Congo red (CR). It was worthy to note that MWCNTs/LDHs exhibited excellent adsorption performance with the maximum CR adsorption capacity of 595.8 mg/g in weak acidic environment. The adsorption kinetics and isotherm parameters can be well described by the pseudo-second-order and the Langmuir isotherm models, respectively. The thermodynamic studies indicated that the adsorption process was spontaneous and endothermic.
基金Project(17JS083) supported by the Key Laboratory Program of Shaanxi Education Department,ChinaProject(2016JZ018) supported by the Key Program of Natural Science Research of Shaanxi Province,ChinaProject(51701162) supported by the National Natural Science Foundation of China
文摘To further enhance the corrosion resistance of the porous micro-arc oxidation(MAO) ceramic layers on AZ31 magnesium alloy, superhydrophobic Mg-Al layered double hydroxide(LDH) coating was fabricated on MAO-coated AZ31 alloy by using in-situ growth method followed by surface modification with stearic acid. The characteristics of different coatings were investigated by XRD, SEM and EDS. The effect of the hydrothermal treatment time on the formation of the LDH coatings was studied. The results demonstrated that the micro-pores and cracks of MAO coating were gradually sealed via in-situ growing LDH with prolonging hydrothermal treating time. Electrochemical measurement displayed that the lowest corrosion current density, the most positive corrosion potential and the highest impedance modulus were observed for superhydrophobic LDH/MAO coating compared with those of MAO coating and LDH/MAO coating. Immersion experiment proved that the superhydrophobic LDH/MAO coating with the active anti-corrosion capability significantly enhanced the long-term corrosion protection for MAO coated alloy.
基金supported by the National Key Research and Development Program(2017YFC0306403)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDA09030104,XDA22010601)the Youth Innovation Promotion Association of the Chinese Academy of Sciences~~
文摘Hydrogen is a promising sustainable energy to replace fossil fuels owning to its high specific energy and environmental friendliness.Alkaline water electrolysis has been considered as one of the most prospective technologies for large scale hydrogen production.To boost the sluggish kinetics of hydrogen evolution reaction(HER)in alkaline media,abundant materials have been designed and fabricated.Herein,we summarize the key achievements in the development of layered transition-metal hydroxides[TM(OH)x]for efficient alkaline HER.Based on the structure of TM(OH)x,the mechanism of synergistic effect between TM(OH)x and HER active materials is illuminated firstly.Then,recent progress of TM(OH)x-based HER catalysts to optimize the synergistic effect are categorized as TM(OH)x and active materials,including species,structure,morphology and interaction relationship.Furthermore,TM(OH)x-based overall water splitting electrocatalysts and electrodes are summarized in the design principles for high activity and stability.Finally,some of key challenges for further developments and applications of hydrogen production are proposed.
文摘Bimetallic nanostructures have attracted great interest as efficient catalyst to enhance activity,selectivity and stability in catalytical conversion.Herein,we report a facile one‐pot carbothermal route to in‐situ controllable synthesize heterogeneous bimetallic Ni3Fe NPs@C nanocatalyst.The X‐ray diffraction,transmission electron microscopy,X‐ray photoelectron spectroscopy and N2 adsorption‐description results reveal that the Ni3Fe alloy nanoparticles are evenly embedded in carbon matrix.The as‐prepared Ni3Fe NPs@C catalyst shows excellent selective hydrogenation catalytic performance toward the conversion of levulinic acid(LA)toγ‐valerolactone(GVL)via both direct hydrogenation(DH)and transfer hydrogenation(TH).In DH of LA,the bimetallic catalyst achieved a 93.8%LA conversion efficiency with a 95.5%GVL selectivity and 38.2 mmol g–1 h–1 GVL productivity(under 130°C,2MPa H2 within 2 h),which are 6 and 40 times in comparison with monometallic Ni NPs@C and Fe NPs@C catalysts,respectively.In addition,the identical catalyst displayed a full conversion of LA with almost 100%GVL selectivity and 167.1 mmol g–1 h–1 GVL productivity at 180°C within 0.5 h in TH of LA.Under optimal reaction conditions,the DH and TH catalytic performance of 500‐Ni3Fe NPs@C(3:1)catalyst for converting LA to GVL is comparable to the state‐of‐the‐art noble‐based catalysts.The demonstrated capability of bimetallic catalyst design approach to introduce dual‐catalytic functionality for DH and TH reactions could be adoptable for other catalysis processes.
文摘Splitting water or reducing CO_(2) via semiconductor photocatalysis to produce H2 or hydrocarbon fuels through the direct utilization of solar energy is a promising approach to mitigating the current fossil fuel energy crisis and environmental challenges.It enables not only the realization of clean,renewable,and high-heating-value solar fuels,but also the reduction of CO_(2) emissions.Layered double hydroxides(LDHs)are a type of two-dimensional anionic clay with a brucite-like structure,and are characterized by a unique,delaminable,multidimensional,layered structure;tunable intralayer metal cations;and exchangeable interlayer guest anions.Therefore,it has been widely investigated in the fields of CO_(2) reduction,photoelectrocatalytic water oxidation,and water photolysis to produce H2.However,the low carrier mobility and poor quantum efficiency of pure LDH limit its application.An increasing number of scholars are exploring methods to obtain LDH-based photocatalysts with high energy conversion efficiency,such as assembling photoactive components into LDH laminates,designing multidimensional structures,or coupling different types of semiconductors to construct heterojunctions.This review first summarizes the main characteristics of LDH,i.e.,metal-cation tunability,intercalated guest-anion substitutability,thermal decomposability,memory effect,multidimensionality,and delaminability.Second,LDHs,LDH-based composites(metal sulfide-LDH composites,metal oxide-LDH composites,graphite phase carbon nitride-LDH composites),ternary LDH-based composites,and mixed-metal oxides for splitting water to produce H_(2) are reviewed.Third,graphite phase carbon nitride-LDH composites,MgAl-LDH composites,CuZn-LDH composites,and other semiconductor-LDH composites for CO_(2) reduction are introduced.Although the field of LDH-based photocatalysts has advanced considerably,the photocatalytic mechanism of LDHs has not been thoroughly elucidated;moreover,the photocatalytic active sites,the synergy between different components,and the interfacial reaction mechanism of LDH-based photocatalysts require further investigation.Therefore,LDH composite materials for photocatalysis could be developed through structural regulation and function-oriented design to investigate the effects of different components and interface reactions,the influence of photogenerated carriers,and the impact of material composition on the physical and chemical properties of the LDH-based photocatalyst.
基金supported by the National Natural Science Foundation of of China(51472191,21407115,21773179)the Natural Science Foundation of Hubei Province of China(2017CFA031)the Opening Project of Key Laboratory of Optoelectronic Chemical Materials and Devices,Ministry of Education(JDGD-201509)~~
文摘Photocatalytic hydrogen production based on semiconductor photocatalysts has been considered as one of the most promising strategies to resolve the global energy shortage.Graphitic carbon nitride(g‐C3N4)has been a star visible‐light photocatalyst in this field due to its various advantages.However,pristine g‐C3N4usually exhibits limited activity.Herein,to enhance the performance of g‐C3N4,alkali metal ion(Li+,Na+,or K+)‐doped g‐C3N4are prepared via facile high‐temperature treatment.The prepared samples are characterized and analyzed using the technique of XRD,ICP‐AES,SEM,UV‐vis DRS,BET,XPS,PL,TRPL,photoelectrochemical measurements,photocatalytic tests,etc.The resultant doped photocatalysts show enhanced visible‐light photocatalytic activities for hydrogen production,benefiting from the increased specific surface areas(which provide more active sites),decreased band gaps for extended visible‐light absorption,and improved electronic structures for efficient charge transfer.In particular,because of the optimal tuning of both microstructure and electronic structure,the Na‐doped g‐C3N4shows the most effective utilization of photogenerated electrons during the water reduction process.As a result,the highest photocatalytic performance is achieved over the Na‐doped g‐C3N4photocatalyst(18.7?mol/h),3.7times that of pristine g‐C3N4(5.0?mol/h).This work gives a systematic study for the understanding of doping effect of alkali metals in semiconductor photocatalysis.
基金Project(51604303) supported by the National Natural Science Foundation of China
文摘To extract selenium(Ⅵ)from the highly caustic leachate of copper anode slime,the Ca-Al-Cl layered double hydroxides(Ca-Al-Cl-LDHs)with a formula of Ca2 Al(OH)6 Cl·2 H2 O by three co-precipitation methods were synthesized.A plate-like morphology and hexagonal crystal structure with typical mineral phases and functional groups were identified by the FESEM,XRD,FTIR,BET and XPS analysis.The forward feeding sample exhibits the best adsorption capacity of Se(Ⅵ).The factor experiments then reveal a favorable adsorption process with low temperature,low NaOH concentration and high adsorbent dosage.Furthermore,the adsorption kinetics and isotherm parameters can be well described by the Langmuir isotherm and the pseudo-second-order models,respectively.Accordingly,the maximum adsorption amount of Se(Ⅵ)onto Ca-Al-Cl-LDHs reaches188.6 mg/g at 50 ℃.
基金supported by the National Natural Science Foundation of China(21322606,21436005,21576095)China Postdoctoral Science Foundation(2016M590771)Guangdong Natural Science Foundation(2016A030310413,2013B090500027,2014A030310445,2016A050502004)~~
文摘Metal-organic-framework (MOF)-based materials with novel physicochemical properties have emerged as promising catalysts for various hydrogenation reactions. In addition to metal clusters and multifunctional organic ligands, MOF-based catalysts can incorporate other functional species, and thus provide various active sites for hydrogenation processes. The structural properties of the catalysts play significant roles in enhancing the interactions among the reactants, products, and catalytic sites, which can be rationally designed. Because of the synergistic effects between the ac-tive sites and the structural properties, MOF-based catalysts can achieve higher activities and selec- tivities in hydrogenation reactions than can be obtained using traditional heterogeneous catalysts. This review provides an overview of recent developments in MOF-based catalysts in the hydro-genation of alkenes, alkynes, nitroarenes, cinnamaldehyde, furfural, benzene, and other compounds. Strategies for improving the catalytic performances of MOF-based catalysts are discussed as well as the different active sites and structural properties of the catalysts.
文摘Photocatalytic hydrogen(H2)evolution is a promising approach for future sustainable energy utilization.However,it is still a great challenge to develop efficient and stable metal‐free photocatalysts with broadband solar absorption in the visible region for H2 production.Metal‐free graphene quantum dot(GQD)is an emerging candidate for this purpose because of its good water‐solubility and tunable band gap.On the other hand,metal phosphides(Ni2P,Co2P,etc)have been demonstrated as novel noble‐metal‐free cocatalysts for water splitting,which can efficiently separate electron‐hole pairs and enhance the photocatalytic activities.Herein,we report for the first time on the use of OH‐functionalized GQDs(OH‐GQDs)photosensitizer coupled with Ni2P nanoparticles for photocatalytic H2 production withλ>420 nm light.The H2 production rate is^94 times higher than that of bare OH‐GQDs,which is even comparable to that of OH‐GQDs with 1.0 wt%Pt cocatalyst.This enhancement is probably due to the semiconductor‐cocatalyst interface interaction between Ni2P and OH‐GQDs to facilitate efficient charge transfer process.
文摘Exploring highly efficient electrochemical water splitting catalysts has recently attracted extensive research interest from both fundamental researches and practical applications.Transition metal‐based layered double hydroxides(LDHs)have been proved to be one of the most efficient materials for oxygen evolution reaction(OER),however,still suffered from low conductivity and sluggish kinetics for hydrogen evolution reaction(HER),which largely inhibited the overall water splitting efficiency.To address this dilemma,enormous approaches including doping regulation,intercalation tuning and defect engineering are therefore rationally designed and developed.Herein,we focus on the recent exciting progress of LDHs hybridization with other two‐dimensional(2D)materials for water splitting reactions,not barely for enhancing OER efficiency but also for boosting HER activity.Particularly,the structural features,morphologies,charge transfer and synergistic effects for the heterostructure/heterointerface that influence the electrocatalytic performance are discussed in details.The hybrid 2D building blocks not only serve as additional conductivity and structural supported but also promote electron transfer at the interfaces and further enhance the electrocatalytic performance.The construction and application of the nanohybrid materials will guide a new direction in developing multifunctional materials based on LDHs,which will contribute to energy conversion and storage.
基金supported by the National Natural Science Foundation of China(91534127,U1463205)the Innovation Scientists and Technicians Troop Construction Projects of Henan Provincethe Chinese Education Ministry 111 Project(B08021)~~
文摘TiO2‐supported Pd‐Sb bimetallic catalysts were prepared and evaluated for the direct synthesis of H2O2 at ambient pressure.The addition of Sb to Pd significantly enhanced catalytic performance,and a Pd50Sb catalyst showed the greatest selectivity of up to 73%.Sb promoted the dispersion of Pd on TiO2,as evidenced by transmission electron microscopy and X‐ray diffraction.X‐ray photoelectron spectroscopy indicated that the oxidation of Pd was suppressed by Sb.In addition,Sb2O3 layers were formed and partially wrapped the surfaces of Pd catalysts,thus suppressing the activation of H2 and subsequent hydrogenation of H2O2.In situ diffuse reflection infrared Fourier transform spectroscopy for CO adsorption suggested that Sb homogenously located on the surface of Pd‐Sb catalysts and isolated contiguous Pd sites,resulting in the rise of the ratio of Pd monomer sites that are favorable for H2O2 formation.As a result,the Sb modified Pd surfaces significantly enhanced the non‐dissociative activation of O2 and H2O2 selectivity.