This paper, an addendum to “Dialectical Thermodynamics’ solution to the conceptual imbroglio that is the reversible path”, this journal, 10, 775-799, was written in response to the requests of several readers to pr...This paper, an addendum to “Dialectical Thermodynamics’ solution to the conceptual imbroglio that is the reversible path”, this journal, 10, 775-799, was written in response to the requests of several readers to provide further evidence of the said “imbroglio”. The evidence here presented relates to the incompatibility existing between the total-entropy and the Gibbs energy prescriptions for the reversible path. The previously published proof of the negentropic nature of the transformation of heat into work is here included to validate out conclusions about the Gibbs energy perspective.展开更多
Taking into consideration the gas compressibility and chemical reaction reversibility, a model was developed to study the interactions between gas flow and chemical reaction in porous media and resolved by the finite ...Taking into consideration the gas compressibility and chemical reaction reversibility, a model was developed to study the interactions between gas flow and chemical reaction in porous media and resolved by the finite volume method on the basis of the gas-solid reaction aA(g)+bB(s)cC(g)+dD(s).The numerical analysis shows that the equilibrium constant is an important factor influencing the process of gas-solid reaction. The stoichiometric coefficients, molar masses of reactant gas, product gas and inert gas are the main factors influencing the density of gas mixture. The equilibrium constant influences the gas flow in porous media obviously when the stoichiometric coefficients satisfy a/c≠1.展开更多
Developing highly active and stable air electrodes remains challenging for reversible solid oxide cells(R-SOCs).Herein,we re-port an A-site high-entropy engineered perovskite oxide,La_(0.2)Pr_(0.2)Nd_(0.2)Ba_(0.2)Sr_(...Developing highly active and stable air electrodes remains challenging for reversible solid oxide cells(R-SOCs).Herein,we re-port an A-site high-entropy engineered perovskite oxide,La_(0.2)Pr_(0.2)Nd_(0.2)Ba_(0.2)Sr_(0.2)Co_(0.8)Fe_(0.2)O_(3−δ)(HE-LSCF),and its electrocatalytic activity and stability property are systematically probed for tubular R-SOCs.The HE-LSCF air electrode exhibits excellent oxygen reduction reac-tion(ORR)activity with a low polarization resistance of 0.042Ω·cm^(2)at 700℃,which is much lower than that of La0.6Sr0.4Co_(0.8)Fe_(0.2)O_(3−δ)(LSCF),indicating the excellent catalytic activity of HE-LSCF.Meanwhile,the tubular R-SOCs with HE-LSCF shows a high peak power density of 1.18 W·cm^(−2)in the fuel cell mode and a promising electrolysis current density of−0.52 A·cm^(−2)at 1.5 V in the electrolysis mode with H_(2)(~10%H_(2)O)atmosphere at 700℃.More importantly,the tubular R-SOCs with HE-LSCF shows favorable stability under 180 h reversible cycling test.Our results show the high-entropy design can significantly enhance the activity and robustness of LSCF electrode for tubular R-SOCs.展开更多
The slow oxygen reaction kinetics of air electrodes impair the performance of reversible protonic ceramic electrochemical cells(R-PCECs);hence,it is imperative to design novel air electrodes featuring excellent cataly...The slow oxygen reaction kinetics of air electrodes impair the performance of reversible protonic ceramic electrochemical cells(R-PCECs);hence,it is imperative to design novel air electrodes featuring excellent catalytic activity and endurance.Here,we report an Rb-doped double perovskite PrBa_(0.8)Ca_(0.1)Rb_(0.1)Co_(2)O_(5+δ)(denoted as PBCR_(0.1)C)as an air electrode for R-PCECs,displaying a low polarization resistance of 0.044Ωcm^(2) at 700℃ and excellent stability during exposure to humid air(3 vol%H_(2)O).The high performance is attributed to the high electrical conductivity,high concentration of oxygen vacancies,and fast surface exchange,as verified by the analyses of X-ray photoelectron spectroscopy,thermogravimetric testing,and conductivity tests.The R-PCECs with the PBCR_(0.1)C air electrode demonstrate an encouraging performance at 700℃:a peak power density of 2.32 W cm^(-2) in a fuel cell(FC)mode and an electrolysis current density of-3.55 A cm^(-2) at 1.3 V in an electrolysis(EL)mode.At 30 vol%steam concentration,a Faraday efficiency of 87.80%and a corresponding H_(2) production rate of 3.05 mL min^(-1) cm^(-2) at a current density of-0.5 A cm^(-2) at 650℃.Additionally,the durability of the cell in the FC mode(120 h),EL mode(120 h),and cycling FC/EL mode(100 h)at 650℃ suggests the great potential of PBCR_(0.1)C as the highly reactive and robust air electrodes of R-PCECs.展开更多
The insufficient stability and poor surface reaction kinetics(i.e.,oxygen reduction reaction(ORR)and oxygen evolution reaction(OER))of air electrodes are significant factors hindering the development of reversible sol...The insufficient stability and poor surface reaction kinetics(i.e.,oxygen reduction reaction(ORR)and oxygen evolution reaction(OER))of air electrodes are significant factors hindering the development of reversible solid oxide cells(R-SOCs).The high-entropy strategy offers a new direction to optimize air electrodes.We introduce a high-entropy air electrode,(La_(0.12)Pr_(0.12)Nd_(0.12)Sm_(0.12)Gd_(0.12))Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)(LPNSGSrCF),demonstrating a low polarization resistance(0.15Ωcm^(2))and good durability(1.3×10^(-3)Ωcm^(2)h^(-1)),superior to those of La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)(0.31Ωcm^(2),2.0×10^(-3)Ωcm^(2)h^(-1))at 650℃.The elevated activity may be a result of the substantial concentration of oxygen vacancies and rapid reaction kinetics,as verified by X-ray photoelectron spectroscopy,electrochemical impedance spectroscopy,and distribution of relaxation times studies.Specifically,an R-SOC with LPNSGSrCF air electrode achieves a peak power density of 1.05 W cm^(-2)in fuel cell mode and a current density of0.89 A cm^(-2)at 1.3 V in electrolysis cell mode(with 30%H_(2)O)at 700℃.Moreover,the cells with LPNSGSrCF electrode can be stably operated in both modes for over 100 h.展开更多
The activation of CO_(2)molecules is a fundamental step for their effective utilization.Constructing highdensity oxygen vacancies on the surface of reducible oxides is pivotal for the activation of CO_(2).In this work...The activation of CO_(2)molecules is a fundamental step for their effective utilization.Constructing highdensity oxygen vacancies on the surface of reducible oxides is pivotal for the activation of CO_(2).In this work,we prepared a series of 0.5PtxCe/Al_(2)O_(3)(x=1,5,10,or 20)catalysts with varying Ce loading and 0.5 wt%of Pt for the reverse water gas shift(RWGS)reaction.The size of CeO_(2)particle increases with Ce loading.Remarkably,the 0.5Pt5Ce/Al_(2)O_(3) catalyst with an average CeO_(2)particle size of 5.5 nm exhibits a very high CO_(2)conversion rate(116.4×10^(-5)mol_(CO_(2))/(g_(cat)·s))and CO selectivity(96.1%)at 600℃.Our experimental findings reveal that the small-size CeO_(2)in 0.5Pt5Ce/Al_(2)O_(3) possesses a greater capacity to generate reactive oxygen vacancies,promoting the adsorption and activation of CO_(2).In addition,the oxygen vacancies are cyclically generated and consumed during the reaction,which contributes to the elevated catalytic performance of the catalyst.This work provides a general strategy to construct rich oxygen vacancies on CeO_(2)for designing high-performance catalysts in C_(1) chemistry.展开更多
Aqueous zinc-ion batteries (AZIBs) are fundamentally challenged by the instability of the electrode/electrolyte interface,predominantly due to irreversible zinc (Zn) deposition and hydrogen evolution.Particularly,the ...Aqueous zinc-ion batteries (AZIBs) are fundamentally challenged by the instability of the electrode/electrolyte interface,predominantly due to irreversible zinc (Zn) deposition and hydrogen evolution.Particularly,the intricate mechanisms behind the electrochemical discrepancies induced by interfacial Zn^(2+)-solvation and deposition behavior demand comprehensive investigation.Organic molecules endowed with special functional groups (such as hydroxyl,carboxyl,etc.) have the potential to significantly optimize the solvation structure of Zn^(2+)and regulate the interfacial electric double layer (EDL).By increasing nucleation overpotential and decreasing interfacial free energy,these functional groups facilitate a lower critical nucleation radius,thereby forming an asymptotic nucleation model to promote uniform Zn deposition.Herein,this study presents a pioneering approach by introducing trace amounts of n-butanol as solvation regulators to engineer the homogenized Zn (H-Zn) anode with a uniform and dense structure.The interfacial reaction and structure evolution are explored by in/ex-situ experimental techniques,indicating that the H-Zn anode exhibits dendrite-free growth,no by-products,and weak hydrogen evolution,in sharp contrast to the bare Zn.Consequently,the H-Zn anode achieves a remarkable Zn utilization rate of approximately 20% and simultaneously sustains a prolonged cycle life exceeding 500 h.Moreover,the H-Zn//NH_(4)V_(4)O^(10)(NVO) full battery showcases exceptional cycle stability,retaining 95.04%capacity retention after 400 cycles at a large current density of 5 A g^(-1).This study enlightens solvation-regulated additives to develop Zn anode with superior utilization efficiency and extended operational lifespan.展开更多
Microarray technology has been widely applied in biomedical research.The key to microarray study is to develop efficient immobilization method.In this study,we designed a new reversible microarray immobilization metho...Microarray technology has been widely applied in biomedical research.The key to microarray study is to develop efficient immobilization method.In this study,we designed a new reversible microarray immobilization method based on thiol-quinone reaction.A quinone-functionalized slide was fabricated through H_(2)O_(2)treatment of dopamine-coated slides.Various thiol-containing molecules can be anchored onto the quinone-functionalized slides via thioether linker,which could be cleaved under H_(2)O_(2) treatment to regenerate quinone groups on the surface.The highly versatile approach can be widely used for immobilization of various thiol-containing molecules.展开更多
This paper compares the irreversible and reversible rate equations from several uni-uni kinetic mechanisms (Michaelis-Menten, Hill and Adair equations) and bi-bi mechanisms (single- and double- displacement equations)...This paper compares the irreversible and reversible rate equations from several uni-uni kinetic mechanisms (Michaelis-Menten, Hill and Adair equations) and bi-bi mechanisms (single- and double- displacement equations). In reversible reactions, Haldane relationship is considered to be identical for all mechanisms considered and reversible equations can be also obtained from this rela- tionship. Some reversible reactions of the metabolism are also presented, with their equilibrium constant.展开更多
The treatment of a multicomponent reversible reaction network is extremely complicated because largenumber of rate constants must be precisely determined and because the calculation based on these rateconstants is ted...The treatment of a multicomponent reversible reaction network is extremely complicated because largenumber of rate constants must be precisely determined and because the calculation based on these rateconstants is tedious.In order to reduce the degrees of freedom of the process,the authors propose a methodin which the reactor and the separator are regarded as a whole.Based on this approach,an N-componentreversible reaction system can be dealt with as a two—component system.Consequently,a simple and ac-cessible way of the apparent rate determination is suggested.For fiist-order reactions,an explicit,simplifiedexpression has been derived for both lumped and distributed parameter reaction systems.展开更多
Metal–N_(2) battery can be applied in both energy storage and electrochemical nitrogen reduction reaction(NRR);however,there has been only extraordinarily little study on metal–N_(2) battery since its electrochemica...Metal–N_(2) battery can be applied in both energy storage and electrochemical nitrogen reduction reaction(NRR);however,there has been only extraordinarily little study on metal–N_(2) battery since its electrochemical reversibility still needs further proofs.And its electrochemical performances also need to be enhanced.Herein,we investigated the discharge–charge reactions between Li anode and N_(2) cathode via designing an efficient catalyst of nanosized SnO_(2) particles dispersed on N-doped carbon nanosheets(SnO 2@NC)for the Li-N_(2) battery,with good cyclic stability and a high specific capacity of 0.25 mA h(~500 mA h g^(−1))at a large current density of 1000 mA g^(−1).The electrochemical reversibility of both NRR in the discharge process and nitrogen extraction reaction in the charge process for Li-N 2 battery is discussed.Time-of-flight secondary ion mass spectrometry results imply that the SnO_(2)@NC can effectively promote the adsorption of N_(2) and the activation of NRR in the discharge process.Furthermore,ex situ X-ray photoelectron spectroscopy and Fourier transform infrared tests are performed to study the electrochemical reversibility of Li-N_(2) battery.It can be proved that the formation and decomposition of discharging product Li_(3)N are electrochemical reversible during cycling in our deigned Li-N_(2) battery system with SnO_(2)@NC catalyst.展开更多
The equations of the second and third order derivative curves of time with respect to potential for a reversible process in adsorption chronopotentiometry are derived and experimentally verified.
The Ni-CeO2 catalysts with different Ni contents were prepared by a co-precipitation method and used for Reverse Water Gas Shift （RWGS） reaction. 2wt.%Ni-CeO2 showed excellent catalytic performance in terms of activ...The Ni-CeO2 catalysts with different Ni contents were prepared by a co-precipitation method and used for Reverse Water Gas Shift （RWGS） reaction. 2wt.%Ni-CeO2 showed excellent catalytic performance in terms of activity, selectivity, and stability for RWGS reaction. Characterizations of the catalyst samples were conducted by XRD and TPR. The results indicated that, in Ni-CeO2 catalysts, there were three kinds of nickel, nickel ions in ceria lattice, highly dispersed NiO and bulk NiO. Oxygen vacancies were formed in CeO2 lattice due to the incorporation of Ni^2＋ ions into ceria lattice. Oxygen vacancies formed in ceria lattice and highly dispersed Ni were key active components for RWGS, and bulk Ni was key active component for methanation of CO2.展开更多
This study investigated 1 wt.% Ni-CeO2 catalysts that were prepared using co-precipitation, deposition-precipitation, and impregnation methods for the reverse water-gas shift （RWGS） reaction. Characterizations of th...This study investigated 1 wt.% Ni-CeO2 catalysts that were prepared using co-precipitation, deposition-precipitation, and impregnation methods for the reverse water-gas shift （RWGS） reaction. Characterizations of the catalyst samples were conducted by Brumauer-Emmett-Teller （BET）, atomic absorption spectrophotometer （AAS）, X-ray diffraction （XRD）, transmission electron microscopy （TEM）, high-resolution transmission electron microscopy （HR-TEM） and temperature programmed reduction （TPR）. The results showed that the Ni-CeO2 catalyst prepared using the co-precipitation method exhibited the best catalytic performance. In the Ni-CeO2 catalyst prepared using co-precipitation method, a combination of highly dispersed NiO and abundant oxygen vacancies was assumed to play a crucial role in determining the catalytic activity and selectivity of the RWGS reaction.展开更多
A series of Ni-CeO2 catalysts were prepared by co-precipitation method with Na2CO3, NaOH, and mixed precipitant （Na2CO3：NaOH; 1：1 ratio） as precipitant, respectively. The effect of the precipitants on the catalyti...A series of Ni-CeO2 catalysts were prepared by co-precipitation method with Na2CO3, NaOH, and mixed precipitant （Na2CO3：NaOH; 1：1 ratio） as precipitant, respectively. The effect of the precipitants on the catalytic performance, physical and chemical properties of Ni-CeO2 catalysts was investigated with the aid of X-ray diffraction （XRD）, Bmmaner-Emmett-Teller method （BET）, Fou- rier-transform infrared spectroscopy （FT-IR）, thermogravimetry （TG）, and H2-TPR characterizations. The Ni-CeO2 catalysts were exam- ined with respect to their catalytic performance for the reverse water-gas shift reaction, and their catalytic activities were ranked as： Ni-CeO2-CP （Na2CO3：NaOH=I：I）〉Ni-CeO2-CP（Na2CO3）〉Ni-CeO2-CP（NaOH）- Correlating to the characteristic results, it was found that the catalyst prepared by co-precipitation with mixed precipitant （Na2CO3：NaOH; 1：1 ratio） as precipitant hadthe most amount of oxygen vacancies accompanied with highly dispersed Ni particles, which made the corresponding Ni-CeO2-CP（Na2CO3：NaOH=I： 1） catalyst exhibit the highest catalytic activity. While the precipitant of Na2CO3 or NaOH resulted in less or no oxygen vacancies in Ni-CeO2 catalysts. As a result, Ni-CeO2-CP（Na2CO3） and Ni-CeO2-CP（NaOH） catalysts presented poor catalytic performance.展开更多
Objective: To detect circulating hepatocellular carcino-ma by demonstrating hepatocellular carcinoma cells orhepatocyte-associated mRNA in the nuclear cell com-ponent of peripheral blood (PBL).Methods: Peripheral bloo...Objective: To detect circulating hepatocellular carcino-ma by demonstrating hepatocellular carcinoma cells orhepatocyte-associated mRNA in the nuclear cell com-ponent of peripheral blood (PBL).Methods: Peripheral blood (5 ml) samples were ob-tained from 93 patients with hepatocellular carcinoma(HCC) and from 33 control subjects (9 with liver cir-rhosis after hepatitis B,14 with chronic hepatitis B,10with normal liver function). To identify HCC cells inperipheral blood, liver-specific human alpha-fetopro-tein (AFP) mRNA was amplified from total RNA ex-tracted from whole blood by reverse transcription-polymerase chain reaction.Results: AFPmRNA was detected in 50 blood samplesfrom the HCC patients (50/93, 53.8%). In contrast,there were no clinical control patients whose samplesshowed detectable AFPmRNA in PBL. The presence ofAFPmRNA in blood seemed to be correlated with thestage (by TNM classification) of HCC, the serum AFPvalue, and the presence of intrahepatic metastasis,portal vein thrombosis, tumor diameter and/or distantmetastasis. In addition, AFPmRNA was detected in theblood of 21 patients with metastasis at extrahepaticorgans (100%) in contrast to 29 (40.3%)of 72 pa-tients without metastasis.Conclusion: The presence of AFPmRNA in peripheralblood may be an indicator of malignant hepatocytes,which might predict hematogenous spreading metasta-sis of tumor cells in patients with HCC.展开更多
Reversible proton ceramic electrochemical cell(R-PCEC)is regarded as the most promising energy conversion device,which can realize efficient mutual conversion of electrical and chemical energy and to solve the problem...Reversible proton ceramic electrochemical cell(R-PCEC)is regarded as the most promising energy conversion device,which can realize efficient mutual conversion of electrical and chemical energy and to solve the problem of large-scale energy storage.However,the development of robust electrodes with high catalytic activity is the main bottleneck for the commercialization of R-PCECs.Here,a novel type of high-entropy perovskite oxide consisting of six equimolar metals in the A-site,Pr_(1/6)La_(1/6)Nd_(1/6)Ba_(1/6)Sr_(1/6)Ca_(1/6)CoO_(3−δ)(PLN-BSCC),is reported as a high-performance bifunctional air electrode for R-PCEC.By harnessing the unique functionalities of multiple ele-ments,high-entropy perovskite oxide can be anticipated to accelerate reaction rates in both fuel cell and electrolysis modes.Especially,an R-PCEC utilizing the PLNBSCC air electrode achieves exceptional electrochemical performances,demonstrating a peak power density of 1.21 W cm^(−2)for the fuel cell,while simultaneously obtaining an astonishing current density of−1.95 A cm^(−2)at an electrolysis voltage of 1.3 V and a temperature of 600℃.The significantly enhanced electrochemical performance and durability of the PLNBSCC air electrode is attributed mainly to the high electrons/ions conductivity,fast hydration reactivity and high configurational entropy.This research explores to a new avenue to develop optimally active and stable air electrodes for R-PCECs.展开更多
The catalytic conversion of CO2 to CO via a reverse water gas shift(RWGS)reaction followed by well-established synthesis gas conversion technologies may provide a potential approach to convert CO2 to valuable chemical...The catalytic conversion of CO2 to CO via a reverse water gas shift(RWGS)reaction followed by well-established synthesis gas conversion technologies may provide a potential approach to convert CO2 to valuable chemicals and fuels.However,this reaction is mildly endothermic and competed by a strongly exothermic CO2 methanation reaction at low temperatures.Therefore,the improvement in the low-temperature activities and selectivity of the RWGS reaction is a key challenge for catalyst designs.We reviewed recent advances in the design strategies of supported metal catalysts for enhancing the activity of CO2 conversion and its selectivity to CO.These strategies include varying support,tuning metal–support interactions,adding reducible transition metal oxide promoters,forming bimetallic alloys,adding alkali metals,and enveloping metal particles.These advances suggest that enhancing CO2 adsorption and facilitating CO desorption are key factors to enhance CO2 conversion and CO selectivity.This short review may provide insights into future RWGS catalyst designs and optimization.展开更多
In reverse water gas shift （RWGS） reaction COa is converted to CO which in turn can be used to pro- duce beneficial chemicals such as methanol. In the present study, Mo/AlaO3, Fe/AlaO3 and Fe-Mo/Al2O3 catalysts were...In reverse water gas shift （RWGS） reaction COa is converted to CO which in turn can be used to pro- duce beneficial chemicals such as methanol. In the present study, Mo/AlaO3, Fe/AlaO3 and Fe-Mo/Al2O3 catalysts were synthesised using impregnation method. The structures of catalysts were studied using X-ray diffraction （XRD）, Brunauer-Emmett-Teller （BET） method, inductively coupled plasma atomic emission spectrometer （ICP-AES）, temperature programmed reduction （H2-TPR）, CO chemisorption, energy dispersive X-ray （EDX） and scanning electron microscopy （SEM） techniques. Kinetic properties of all catalysts were investigated in a batch re- actor for RWGS reaction. The results indicated that Mo existence in structure of Fe-Mo/AlzO3 catalyst enhances its activity as compared to Fe/AlaO3. This enhancement is probably due to better Fe dispersion and smaller particle size of Fe species. Stability test of Fe-Mo/AlzO3 catalyst was carried out in a fixed bed reactor and a high CO yield for 60 h of time on stream was demonstrated. Fez（MoO4）3 phase was found in the structures of fresh and used catalysts. TPR results also indicate that Fez（MoO4）3 phase has low reducibility, therefore the Fe2（MoO4）3 phase significantly inhibits the reduction of the remaining Fe oxides in the catalyst, resulted in high stability of Fe-Mo/Al2O3 catalyst. Overall, this study introduces Fe-Mo/Al2O3 as a novel catalyst with high CO yield, almost no by-products and fairly stable for RWGS reaction.展开更多
Ammonium vanadate with bronze structure(NH_(4)V_(4)O_(10))is a promising cathode material for zinc-ion batteries due to its high specific capacity and low cost.However,the extraction of NH^(+)_(4) at a high voltage du...Ammonium vanadate with bronze structure(NH_(4)V_(4)O_(10))is a promising cathode material for zinc-ion batteries due to its high specific capacity and low cost.However,the extraction of NH^(+)_(4) at a high voltage during charge/discharge processes leads to irreversible reaction and structure degradation.In this work,partial NH^(+)_(4) ions were pre-removed from NH_(4)V_(4)O_(10) through heat treatment;NH_(4)V_(4)O_(10) nanosheets were directly grown on carbon cloth through hydrothermal method.Defi-cient NH_(4)V_(4)O_(10)(denoted as NVO),with enlarged interlayer spacing,facilitated fast zinc ions transport and high storage capacity and ensured the highly reversible electrochemical reaction and the good stability of layered structure.The NVO nanosheets delivered a high specific capac-ity of 457 mAh g^(−1) at a current density of 100 mA g^(−1) and a capacity retention of 81%over 1000 cycles at 2 A g^(−1).The initial Coulombic efficiency of NVO could reach up to 97%compared to 85%of NH_(4)V_(4)O_(10) and maintain almost 100%during cycling,indicating the high reaction reversibility in NVO electrode.展开更多
文摘This paper, an addendum to “Dialectical Thermodynamics’ solution to the conceptual imbroglio that is the reversible path”, this journal, 10, 775-799, was written in response to the requests of several readers to provide further evidence of the said “imbroglio”. The evidence here presented relates to the incompatibility existing between the total-entropy and the Gibbs energy prescriptions for the reversible path. The previously published proof of the negentropic nature of the transformation of heat into work is here included to validate out conclusions about the Gibbs energy perspective.
基金Projects(51304035,50974030)supported by the National Natural Science Foundation of ChinaProject(20110491512)supported by the Postdoctoral Science Foundation of China+2 种基金Project(20130042120034)supported by the Specialized Research Fund for the Doctoral Program of Higher Education(New Teachers),ChinaProject(120401008)supported by the Fundamental Research Funds for Central Universities,ChinaProject(L20150173)supported by the Scientific Research Fund of Liaoning Provincial Education Department,China
文摘Taking into consideration the gas compressibility and chemical reaction reversibility, a model was developed to study the interactions between gas flow and chemical reaction in porous media and resolved by the finite volume method on the basis of the gas-solid reaction aA(g)+bB(s)cC(g)+dD(s).The numerical analysis shows that the equilibrium constant is an important factor influencing the process of gas-solid reaction. The stoichiometric coefficients, molar masses of reactant gas, product gas and inert gas are the main factors influencing the density of gas mixture. The equilibrium constant influences the gas flow in porous media obviously when the stoichiometric coefficients satisfy a/c≠1.
基金support provided by the National Key R&D Program of China(No.2024YFE0101500)the National Natural Science Foundation of China(No.52272257)the Natural Science Foundation of Jiangsu Province(No.BK20240109).
文摘Developing highly active and stable air electrodes remains challenging for reversible solid oxide cells(R-SOCs).Herein,we re-port an A-site high-entropy engineered perovskite oxide,La_(0.2)Pr_(0.2)Nd_(0.2)Ba_(0.2)Sr_(0.2)Co_(0.8)Fe_(0.2)O_(3−δ)(HE-LSCF),and its electrocatalytic activity and stability property are systematically probed for tubular R-SOCs.The HE-LSCF air electrode exhibits excellent oxygen reduction reac-tion(ORR)activity with a low polarization resistance of 0.042Ω·cm^(2)at 700℃,which is much lower than that of La0.6Sr0.4Co_(0.8)Fe_(0.2)O_(3−δ)(LSCF),indicating the excellent catalytic activity of HE-LSCF.Meanwhile,the tubular R-SOCs with HE-LSCF shows a high peak power density of 1.18 W·cm^(−2)in the fuel cell mode and a promising electrolysis current density of−0.52 A·cm^(−2)at 1.5 V in the electrolysis mode with H_(2)(~10%H_(2)O)atmosphere at 700℃.More importantly,the tubular R-SOCs with HE-LSCF shows favorable stability under 180 h reversible cycling test.Our results show the high-entropy design can significantly enhance the activity and robustness of LSCF electrode for tubular R-SOCs.
文摘The slow oxygen reaction kinetics of air electrodes impair the performance of reversible protonic ceramic electrochemical cells(R-PCECs);hence,it is imperative to design novel air electrodes featuring excellent catalytic activity and endurance.Here,we report an Rb-doped double perovskite PrBa_(0.8)Ca_(0.1)Rb_(0.1)Co_(2)O_(5+δ)(denoted as PBCR_(0.1)C)as an air electrode for R-PCECs,displaying a low polarization resistance of 0.044Ωcm^(2) at 700℃ and excellent stability during exposure to humid air(3 vol%H_(2)O).The high performance is attributed to the high electrical conductivity,high concentration of oxygen vacancies,and fast surface exchange,as verified by the analyses of X-ray photoelectron spectroscopy,thermogravimetric testing,and conductivity tests.The R-PCECs with the PBCR_(0.1)C air electrode demonstrate an encouraging performance at 700℃:a peak power density of 2.32 W cm^(-2) in a fuel cell(FC)mode and an electrolysis current density of-3.55 A cm^(-2) at 1.3 V in an electrolysis(EL)mode.At 30 vol%steam concentration,a Faraday efficiency of 87.80%and a corresponding H_(2) production rate of 3.05 mL min^(-1) cm^(-2) at a current density of-0.5 A cm^(-2) at 650℃.Additionally,the durability of the cell in the FC mode(120 h),EL mode(120 h),and cycling FC/EL mode(100 h)at 650℃ suggests the great potential of PBCR_(0.1)C as the highly reactive and robust air electrodes of R-PCECs.
基金supported by the National Key R&D Program of China(2022YFB4003601)the National Natural Science Foundation of China(22179039)+4 种基金the Introduced Innovative R&D Team of Guangdong(2021ZT09L392)the Guangzhou Science and Technology Project(2024A04J3079)the Guangdong Basic and Applied Basic Research Foundation(2024A1515010448)the Pearl River Talent Recruitment Program(2019QN01C693)Zijin Mining Group Co.,Ltd(5405-ZC-2023-00008).
文摘The insufficient stability and poor surface reaction kinetics(i.e.,oxygen reduction reaction(ORR)and oxygen evolution reaction(OER))of air electrodes are significant factors hindering the development of reversible solid oxide cells(R-SOCs).The high-entropy strategy offers a new direction to optimize air electrodes.We introduce a high-entropy air electrode,(La_(0.12)Pr_(0.12)Nd_(0.12)Sm_(0.12)Gd_(0.12))Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)(LPNSGSrCF),demonstrating a low polarization resistance(0.15Ωcm^(2))and good durability(1.3×10^(-3)Ωcm^(2)h^(-1)),superior to those of La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)(0.31Ωcm^(2),2.0×10^(-3)Ωcm^(2)h^(-1))at 650℃.The elevated activity may be a result of the substantial concentration of oxygen vacancies and rapid reaction kinetics,as verified by X-ray photoelectron spectroscopy,electrochemical impedance spectroscopy,and distribution of relaxation times studies.Specifically,an R-SOC with LPNSGSrCF air electrode achieves a peak power density of 1.05 W cm^(-2)in fuel cell mode and a current density of0.89 A cm^(-2)at 1.3 V in electrolysis cell mode(with 30%H_(2)O)at 700℃.Moreover,the cells with LPNSGSrCF electrode can be stably operated in both modes for over 100 h.
基金Project supported by the National Science Fund for Distinguished Young Scholars of China(22225110)the National Key Research and Development Program of China(2021YFA1501103)+1 种基金the National Science Foundation of China(22075166,22271177)the Young Scholars Program of Shandong University。
文摘The activation of CO_(2)molecules is a fundamental step for their effective utilization.Constructing highdensity oxygen vacancies on the surface of reducible oxides is pivotal for the activation of CO_(2).In this work,we prepared a series of 0.5PtxCe/Al_(2)O_(3)(x=1,5,10,or 20)catalysts with varying Ce loading and 0.5 wt%of Pt for the reverse water gas shift(RWGS)reaction.The size of CeO_(2)particle increases with Ce loading.Remarkably,the 0.5Pt5Ce/Al_(2)O_(3) catalyst with an average CeO_(2)particle size of 5.5 nm exhibits a very high CO_(2)conversion rate(116.4×10^(-5)mol_(CO_(2))/(g_(cat)·s))and CO selectivity(96.1%)at 600℃.Our experimental findings reveal that the small-size CeO_(2)in 0.5Pt5Ce/Al_(2)O_(3) possesses a greater capacity to generate reactive oxygen vacancies,promoting the adsorption and activation of CO_(2).In addition,the oxygen vacancies are cyclically generated and consumed during the reaction,which contributes to the elevated catalytic performance of the catalyst.This work provides a general strategy to construct rich oxygen vacancies on CeO_(2)for designing high-performance catalysts in C_(1) chemistry.
基金National Natural Science Foundation of China (52301273, 52072411)Science and Technology Innovation Program of Hunan Province (2024RC3222)+3 种基金Key project of scientific research project of Hunan Provincial Department of Education (22A0479)China Postdoctoral Science Foundation (2024M753668)Central South University Innovation-Driven Research Programme (2023CXQD038)Hunan Provincial Postgraduate Research Innovation Programme(CX20240970)。
文摘Aqueous zinc-ion batteries (AZIBs) are fundamentally challenged by the instability of the electrode/electrolyte interface,predominantly due to irreversible zinc (Zn) deposition and hydrogen evolution.Particularly,the intricate mechanisms behind the electrochemical discrepancies induced by interfacial Zn^(2+)-solvation and deposition behavior demand comprehensive investigation.Organic molecules endowed with special functional groups (such as hydroxyl,carboxyl,etc.) have the potential to significantly optimize the solvation structure of Zn^(2+)and regulate the interfacial electric double layer (EDL).By increasing nucleation overpotential and decreasing interfacial free energy,these functional groups facilitate a lower critical nucleation radius,thereby forming an asymptotic nucleation model to promote uniform Zn deposition.Herein,this study presents a pioneering approach by introducing trace amounts of n-butanol as solvation regulators to engineer the homogenized Zn (H-Zn) anode with a uniform and dense structure.The interfacial reaction and structure evolution are explored by in/ex-situ experimental techniques,indicating that the H-Zn anode exhibits dendrite-free growth,no by-products,and weak hydrogen evolution,in sharp contrast to the bare Zn.Consequently,the H-Zn anode achieves a remarkable Zn utilization rate of approximately 20% and simultaneously sustains a prolonged cycle life exceeding 500 h.Moreover,the H-Zn//NH_(4)V_(4)O^(10)(NVO) full battery showcases exceptional cycle stability,retaining 95.04%capacity retention after 400 cycles at a large current density of 5 A g^(-1).This study enlightens solvation-regulated additives to develop Zn anode with superior utilization efficiency and extended operational lifespan.
基金the financial support from the Research Grants Council of Hong Kong(Nos.11102719,11304118 and 14306317)Shenzhen Basic Research Project(No.JCYJ20160601173218804)+1 种基金National Natural Science Foundation of China(No.21778044)the Shandong University of Technology Ph.D.Startup Foundation(No.420033)。
文摘Microarray technology has been widely applied in biomedical research.The key to microarray study is to develop efficient immobilization method.In this study,we designed a new reversible microarray immobilization method based on thiol-quinone reaction.A quinone-functionalized slide was fabricated through H_(2)O_(2)treatment of dopamine-coated slides.Various thiol-containing molecules can be anchored onto the quinone-functionalized slides via thioether linker,which could be cleaved under H_(2)O_(2) treatment to regenerate quinone groups on the surface.The highly versatile approach can be widely used for immobilization of various thiol-containing molecules.
文摘This paper compares the irreversible and reversible rate equations from several uni-uni kinetic mechanisms (Michaelis-Menten, Hill and Adair equations) and bi-bi mechanisms (single- and double- displacement equations). In reversible reactions, Haldane relationship is considered to be identical for all mechanisms considered and reversible equations can be also obtained from this rela- tionship. Some reversible reactions of the metabolism are also presented, with their equilibrium constant.
文摘The treatment of a multicomponent reversible reaction network is extremely complicated because largenumber of rate constants must be precisely determined and because the calculation based on these rateconstants is tedious.In order to reduce the degrees of freedom of the process,the authors propose a methodin which the reactor and the separator are regarded as a whole.Based on this approach,an N-componentreversible reaction system can be dealt with as a two—component system.Consequently,a simple and ac-cessible way of the apparent rate determination is suggested.For fiist-order reactions,an explicit,simplifiedexpression has been derived for both lumped and distributed parameter reaction systems.
基金This work was financially supported by the National Natural Science Foundation of China (52071144,51621001,and 51822104).
文摘Metal–N_(2) battery can be applied in both energy storage and electrochemical nitrogen reduction reaction(NRR);however,there has been only extraordinarily little study on metal–N_(2) battery since its electrochemical reversibility still needs further proofs.And its electrochemical performances also need to be enhanced.Herein,we investigated the discharge–charge reactions between Li anode and N_(2) cathode via designing an efficient catalyst of nanosized SnO_(2) particles dispersed on N-doped carbon nanosheets(SnO 2@NC)for the Li-N_(2) battery,with good cyclic stability and a high specific capacity of 0.25 mA h(~500 mA h g^(−1))at a large current density of 1000 mA g^(−1).The electrochemical reversibility of both NRR in the discharge process and nitrogen extraction reaction in the charge process for Li-N 2 battery is discussed.Time-of-flight secondary ion mass spectrometry results imply that the SnO_(2)@NC can effectively promote the adsorption of N_(2) and the activation of NRR in the discharge process.Furthermore,ex situ X-ray photoelectron spectroscopy and Fourier transform infrared tests are performed to study the electrochemical reversibility of Li-N_(2) battery.It can be proved that the formation and decomposition of discharging product Li_(3)N are electrochemical reversible during cycling in our deigned Li-N_(2) battery system with SnO_(2)@NC catalyst.
文摘The equations of the second and third order derivative curves of time with respect to potential for a reversible process in adsorption chronopotentiometry are derived and experimentally verified.
基金Project supported by the National Natural Science Foundation of China (20476079)
文摘The Ni-CeO2 catalysts with different Ni contents were prepared by a co-precipitation method and used for Reverse Water Gas Shift （RWGS） reaction. 2wt.%Ni-CeO2 showed excellent catalytic performance in terms of activity, selectivity, and stability for RWGS reaction. Characterizations of the catalyst samples were conducted by XRD and TPR. The results indicated that, in Ni-CeO2 catalysts, there were three kinds of nickel, nickel ions in ceria lattice, highly dispersed NiO and bulk NiO. Oxygen vacancies were formed in CeO2 lattice due to the incorporation of Ni^2＋ ions into ceria lattice. Oxygen vacancies formed in ceria lattice and highly dispersed Ni were key active components for RWGS, and bulk Ni was key active component for methanation of CO2.
基金supported by the Foundation of Natural Science of Zhejiang Province(Y4110220)Foundation of the Zhejiang Provincial Department of Education(Y200908245)
文摘This study investigated 1 wt.% Ni-CeO2 catalysts that were prepared using co-precipitation, deposition-precipitation, and impregnation methods for the reverse water-gas shift （RWGS） reaction. Characterizations of the catalyst samples were conducted by Brumauer-Emmett-Teller （BET）, atomic absorption spectrophotometer （AAS）, X-ray diffraction （XRD）, transmission electron microscopy （TEM）, high-resolution transmission electron microscopy （HR-TEM） and temperature programmed reduction （TPR）. The results showed that the Ni-CeO2 catalyst prepared using the co-precipitation method exhibited the best catalytic performance. In the Ni-CeO2 catalyst prepared using co-precipitation method, a combination of highly dispersed NiO and abundant oxygen vacancies was assumed to play a crucial role in determining the catalytic activity and selectivity of the RWGS reaction.
基金Project supported by Natural Science Foundation of Zhejiang Province(Y4110220)Foundation of the Zhejiang Provincial Department of Education(Y200908245)Foundation of the Dinghai Academy of Science and Technology(201006)
文摘A series of Ni-CeO2 catalysts were prepared by co-precipitation method with Na2CO3, NaOH, and mixed precipitant （Na2CO3：NaOH; 1：1 ratio） as precipitant, respectively. The effect of the precipitants on the catalytic performance, physical and chemical properties of Ni-CeO2 catalysts was investigated with the aid of X-ray diffraction （XRD）, Bmmaner-Emmett-Teller method （BET）, Fou- rier-transform infrared spectroscopy （FT-IR）, thermogravimetry （TG）, and H2-TPR characterizations. The Ni-CeO2 catalysts were exam- ined with respect to their catalytic performance for the reverse water-gas shift reaction, and their catalytic activities were ranked as： Ni-CeO2-CP （Na2CO3：NaOH=I：I）〉Ni-CeO2-CP（Na2CO3）〉Ni-CeO2-CP（NaOH）- Correlating to the characteristic results, it was found that the catalyst prepared by co-precipitation with mixed precipitant （Na2CO3：NaOH; 1：1 ratio） as precipitant hadthe most amount of oxygen vacancies accompanied with highly dispersed Ni particles, which made the corresponding Ni-CeO2-CP（Na2CO3：NaOH=I： 1） catalyst exhibit the highest catalytic activity. While the precipitant of Na2CO3 or NaOH resulted in less or no oxygen vacancies in Ni-CeO2 catalysts. As a result, Ni-CeO2-CP（Na2CO3） and Ni-CeO2-CP（NaOH） catalysts presented poor catalytic performance.
文摘Objective: To detect circulating hepatocellular carcino-ma by demonstrating hepatocellular carcinoma cells orhepatocyte-associated mRNA in the nuclear cell com-ponent of peripheral blood (PBL).Methods: Peripheral blood (5 ml) samples were ob-tained from 93 patients with hepatocellular carcinoma(HCC) and from 33 control subjects (9 with liver cir-rhosis after hepatitis B,14 with chronic hepatitis B,10with normal liver function). To identify HCC cells inperipheral blood, liver-specific human alpha-fetopro-tein (AFP) mRNA was amplified from total RNA ex-tracted from whole blood by reverse transcription-polymerase chain reaction.Results: AFPmRNA was detected in 50 blood samplesfrom the HCC patients (50/93, 53.8%). In contrast,there were no clinical control patients whose samplesshowed detectable AFPmRNA in PBL. The presence ofAFPmRNA in blood seemed to be correlated with thestage (by TNM classification) of HCC, the serum AFPvalue, and the presence of intrahepatic metastasis,portal vein thrombosis, tumor diameter and/or distantmetastasis. In addition, AFPmRNA was detected in theblood of 21 patients with metastasis at extrahepaticorgans (100%) in contrast to 29 (40.3%)of 72 pa-tients without metastasis.Conclusion: The presence of AFPmRNA in peripheralblood may be an indicator of malignant hepatocytes,which might predict hematogenous spreading metasta-sis of tumor cells in patients with HCC.
基金The work was supported by National Natural Science Foundation of China(21878158 and 21706129)State Key Laboratory of Clean Energy Utilization(Open Fund Project No.ZJUCEU2021001)Natural Science Foundation of Jiangsu Province(BK20221312).
文摘Reversible proton ceramic electrochemical cell(R-PCEC)is regarded as the most promising energy conversion device,which can realize efficient mutual conversion of electrical and chemical energy and to solve the problem of large-scale energy storage.However,the development of robust electrodes with high catalytic activity is the main bottleneck for the commercialization of R-PCECs.Here,a novel type of high-entropy perovskite oxide consisting of six equimolar metals in the A-site,Pr_(1/6)La_(1/6)Nd_(1/6)Ba_(1/6)Sr_(1/6)Ca_(1/6)CoO_(3−δ)(PLN-BSCC),is reported as a high-performance bifunctional air electrode for R-PCEC.By harnessing the unique functionalities of multiple ele-ments,high-entropy perovskite oxide can be anticipated to accelerate reaction rates in both fuel cell and electrolysis modes.Especially,an R-PCEC utilizing the PLNBSCC air electrode achieves exceptional electrochemical performances,demonstrating a peak power density of 1.21 W cm^(−2)for the fuel cell,while simultaneously obtaining an astonishing current density of−1.95 A cm^(−2)at an electrolysis voltage of 1.3 V and a temperature of 600℃.The significantly enhanced electrochemical performance and durability of the PLNBSCC air electrode is attributed mainly to the high electrons/ions conductivity,fast hydration reactivity and high configurational entropy.This research explores to a new avenue to develop optimally active and stable air electrodes for R-PCECs.
基金the National Key Research and Development Program of China(No.2016YFB0600900)the National Natural Science Foundation of China(Nos.21676194 and 21873067)for their support。
文摘The catalytic conversion of CO2 to CO via a reverse water gas shift(RWGS)reaction followed by well-established synthesis gas conversion technologies may provide a potential approach to convert CO2 to valuable chemicals and fuels.However,this reaction is mildly endothermic and competed by a strongly exothermic CO2 methanation reaction at low temperatures.Therefore,the improvement in the low-temperature activities and selectivity of the RWGS reaction is a key challenge for catalyst designs.We reviewed recent advances in the design strategies of supported metal catalysts for enhancing the activity of CO2 conversion and its selectivity to CO.These strategies include varying support,tuning metal–support interactions,adding reducible transition metal oxide promoters,forming bimetallic alloys,adding alkali metals,and enveloping metal particles.These advances suggest that enhancing CO2 adsorption and facilitating CO desorption are key factors to enhance CO2 conversion and CO selectivity.This short review may provide insights into future RWGS catalyst designs and optimization.
基金Supported by the Iranian Nano Technology Initiative Council and Petroleum University of Technology
文摘In reverse water gas shift （RWGS） reaction COa is converted to CO which in turn can be used to pro- duce beneficial chemicals such as methanol. In the present study, Mo/AlaO3, Fe/AlaO3 and Fe-Mo/Al2O3 catalysts were synthesised using impregnation method. The structures of catalysts were studied using X-ray diffraction （XRD）, Brunauer-Emmett-Teller （BET） method, inductively coupled plasma atomic emission spectrometer （ICP-AES）, temperature programmed reduction （H2-TPR）, CO chemisorption, energy dispersive X-ray （EDX） and scanning electron microscopy （SEM） techniques. Kinetic properties of all catalysts were investigated in a batch re- actor for RWGS reaction. The results indicated that Mo existence in structure of Fe-Mo/AlzO3 catalyst enhances its activity as compared to Fe/AlaO3. This enhancement is probably due to better Fe dispersion and smaller particle size of Fe species. Stability test of Fe-Mo/AlzO3 catalyst was carried out in a fixed bed reactor and a high CO yield for 60 h of time on stream was demonstrated. Fez（MoO4）3 phase was found in the structures of fresh and used catalysts. TPR results also indicate that Fez（MoO4）3 phase has low reducibility, therefore the Fe2（MoO4）3 phase significantly inhibits the reduction of the remaining Fe oxides in the catalyst, resulted in high stability of Fe-Mo/Al2O3 catalyst. Overall, this study introduces Fe-Mo/Al2O3 as a novel catalyst with high CO yield, almost no by-products and fairly stable for RWGS reaction.
基金This work was supported by the National Science Foundation(CBET-1803256)National Natural Science Foundation of China(Grant No.51772267)+3 种基金the National Key R&D Program of China(Grant No.2016YFB0401501)the Key R&D Program of Zhejiang Province(Grant No.2020C01004)The author acknowledges the financial support from China Scholarship Council(No.201906320198)2019 Zhejiang University Academic Award for Outstanding Doctoral Candidates.
文摘Ammonium vanadate with bronze structure(NH_(4)V_(4)O_(10))is a promising cathode material for zinc-ion batteries due to its high specific capacity and low cost.However,the extraction of NH^(+)_(4) at a high voltage during charge/discharge processes leads to irreversible reaction and structure degradation.In this work,partial NH^(+)_(4) ions were pre-removed from NH_(4)V_(4)O_(10) through heat treatment;NH_(4)V_(4)O_(10) nanosheets were directly grown on carbon cloth through hydrothermal method.Defi-cient NH_(4)V_(4)O_(10)(denoted as NVO),with enlarged interlayer spacing,facilitated fast zinc ions transport and high storage capacity and ensured the highly reversible electrochemical reaction and the good stability of layered structure.The NVO nanosheets delivered a high specific capac-ity of 457 mAh g^(−1) at a current density of 100 mA g^(−1) and a capacity retention of 81%over 1000 cycles at 2 A g^(−1).The initial Coulombic efficiency of NVO could reach up to 97%compared to 85%of NH_(4)V_(4)O_(10) and maintain almost 100%during cycling,indicating the high reaction reversibility in NVO electrode.
