Electrochemical C-C and C-N coupling reactions with the conversion of abundant and inexpensive small molecules,such as CO_(2) and nitrogencontaining species,are considered a promising route for increasing the value of...Electrochemical C-C and C-N coupling reactions with the conversion of abundant and inexpensive small molecules,such as CO_(2) and nitrogencontaining species,are considered a promising route for increasing the value of CO_(2) reduction products.The development of high-performance catalysts is the key to the both electrocatalytic reactions.In this review,we present a systematic summary of the reaction systems for electrocatalytic CO_(2) reduction,along with the coupling mechanisms of C-C and C-N bonds over outstanding electrocatalytic materials recently developed.The key intermediate species and reaction pathways related to the coupling as well as the catalyst-structure relationship will be also discussed,aiming to provide insights and guidance for designing efficient CO_(2) reduction systems.展开更多
Photothermal catalytic CO_(2) conversion provides an effective solution targeting carbon neutrality by synergistic utilization of photon and heat.However,the C-C coupling initiated by photothermal catalysis is still a...Photothermal catalytic CO_(2) conversion provides an effective solution targeting carbon neutrality by synergistic utilization of photon and heat.However,the C-C coupling initiated by photothermal catalysis is still a big challenge.Herein,a three-dimensional(3D)hierarchical W_(18)O_(49)/WTe_(2) hollow nanosphere is constructed through in-situ embodying of oxygen vacancy and tellurium on the scaffold of WO_(3).The light absorption towards near-infrared spectral region and CO_(2) adsorption are enhanced by the formation of half-metal WTe_(2) and the unique hierarchical hollow architecture.Combining with the generation of oxygen vacancy with strengthened CO_(2) capture,the photothermal effect on the samples can be sufficiently exploited for activating the CO_(2) molecules.In particular,the close contact between W_(18)O_(49)and WTe_(2) largely promotes the photoinduced charge separation and mass transfer,and thus the~*CHO intermediate formation and fixedness are facilitated.As a result,the C-C coupling can be evoked between tungsten and tellurium atoms on WTe_(2).The ethylene production by optimized W_(18)O_(49)/WTe_(2) reaches 147.6μmol g^(-1)with the selectivity of 80%.The in-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)and density functional theory(DFT)calculations are performed to unveil the presence and significance of aldehyde intermediate groups in C-C coupling.The half-metallic WTe_(2) cocatalyst proposes a new approach for efficient CO_(2) conversion with solar energy,and may especially create a new platform for the generation of multi-carbon products.展开更多
Steering the directional carrier migration across the interface is a central mission for efficient photocatalytic reactions.In this work,an atomic-shared heterointerface is constructed between the defect-rich ZnIn_(2)...Steering the directional carrier migration across the interface is a central mission for efficient photocatalytic reactions.In this work,an atomic-shared heterointerface is constructed between the defect-rich ZnIn_(2)S_(4)(HVs-ZIS)and CoIn_(2)S_(4)(CIS)via a defect-guided heteroepitaxial growth strategy.The strong interface coupling induces adequate carriers exchanging passageway between HVs-ZIS and CIS,enhancing the internal electric field(IEF)in the ZnIn_(2)S_(4)/CoIn_(2)S_(4)(HVs-ZIS/CIS)heterostructure.The defect structure in HVs-ZIS induces an additional defect level,improving the separation efficiency of photocarriers.Moreover,promoted by the IEF and intimate heterointerface,photogenerated electrons trapped by the defect level can migrate to the valence band of CIS,contributing to massive photogenerated electrons with intense reducibility in HVs-ZIS/CIS.Consequently,the HVs-ZIS/CIS heterostructure performs a boosted H_(2)evolution activity of 33.65 mmol g^(-1)h^(-1).This work highlights the synergistic effects of defect and strong interface coupling in regulating carrier transfer and paves a brave avenue for constructing efficient heterostructure photocatalysts.展开更多
High qualityβ-Ga_(2)O_(3)single crystal nanobelts with length of 2−3 mm and width from tens of microns to 132μm were synthesized by carbothermal reduction method.Based on the grown nanobelt with the length of 600μm...High qualityβ-Ga_(2)O_(3)single crystal nanobelts with length of 2−3 mm and width from tens of microns to 132μm were synthesized by carbothermal reduction method.Based on the grown nanobelt with the length of 600μm,the dual-Schottky-junctions coupling device(DSCD)was fabricated.Due to the electrically floating Ga_(2)O_(3)nanobelt region coupling with the double Schottky-junctions,the current I_(S2)increases firstly and rapidly reaches into saturation as increase the voltage V_(S2).The saturation current is about 10 pA,which is two orders of magnitude lower than that of a single Schottky-junction.In the case of solar-blind ultraviolet(UV)light irradiation,the photogenerated electrons further aggravate the coupling physical mechanism in device.I_(S2)increases as the intensity of UV light increases.Under the UV light of 1820μW/cm^(2),I_(S2)quickly enters the saturation state.At V_(S2)=10 V,photo-to-dark current ratio(PDCR)of the device reaches more than 104,the external quantum efficiency(EQE)is 1.6×10^(3)%,and the detectivity(D*)is 7.5×10^(12)Jones.In addition,the device has a very short rise and decay times of 25−54 ms under different positive and negative bias.DSCD shows unique electrical and optical control characteristics,which will open a new way for the application of nanobelt-based devices.展开更多
The elastic and functional coupling of heart and vessels makes the stroke work (SW) of the heart optimal. Speckle tracking imaging (STI) can evaluate the myocardial strain and function. We studied ventricular-vasc...The elastic and functional coupling of heart and vessels makes the stroke work (SW) of the heart optimal. Speckle tracking imaging (STI) can evaluate the myocardial strain and function. We studied ventricular-vascular coupling in 80 diabetic patients with different systolic function using STI. The patients were divided into two groups according to ejection fraction (EF): the diabetes mel- litus with normal EF (DMN) group and the diabetes mellitus with abnormal EF (DMA) group. Forty-two volunteers served as control group. The relative wall thickness (RWT), left ventricular mass index (LVMI), stroke volume (SV), SW, rate-pressure product (RPP), systemic vascular resis- tance index (SVRI), left ventricular end-systolic elastance (Ees), effective arterial elasticity (Ea) and ventricular-vascular coupling index (VVI) were measured and calculated by conventional echocardi- ography. The longitudinal strain (LS) at basement (LSBA), papillary muscle (LSvM) and cardiac apex (LSAv) was assessed with STI. It was found: (A) compared with control group, in DMN and DMA groups, LSBA, LSvM and LSAp decreased, and they were lower in DMA group. (B) VVI, RPP and SVRI increased, and they were higher in DMN group; Ees decreased, and it was lower in DMA group. (C) LSBA, LSpM, and LSAv had negative correlation with VVI. LSAp, RWT, LVMI and SW were independent predictors for VVI. The area under the receiver operating characteristic (ROC) curves was used for identification of DMA and DMN with LSBA, LSpM, and LSAp, and the area under the ROC of LSAp was the largest. This study supports that myocardial LS could reflect the ventricu- lar-vascular coupling. Different segments had an order to “respond to” the state of the coupling, and the cardiac apex might be the earliest.展开更多
Cu-based catalysts are the most promising candidates for electrochemical CO_(2)reduction(CO_(2)RR)to multi-carbon(C_(2))products.Optimizing the C-C coupling process,the rate-determining step for C_(2)product generatio...Cu-based catalysts are the most promising candidates for electrochemical CO_(2)reduction(CO_(2)RR)to multi-carbon(C_(2))products.Optimizing the C-C coupling process,the rate-determining step for C_(2)product generation,is an important strategy to improve the production and selectivity of the C_(2)products.In this study,we determined that the local electric field can promote the C-C coupling reaction and enhance CO_(2)electroreduction to C_(2)products.First,finite-element simulations indicated that the high curvature of the Cu nanoneedles results in a large local electric field on their tips.Density functional theory(DFT)calculations proved that a large electric field can promote C-C coupling.Motivated by this prediction,we prepared a series of Cu catalysts with different curvatures.The Cu nanoneedles(NNs)exhibited the largest number of curvatures,followed by the Cu nanorods(NRs),and Cu nanoparticles(NPs).The Cu NNs contained the highest concentration of adsorbed K+,which resulted in the highest local electric field on the needles.CO adsorption sensor tests indicated that the Cu NNs exhibited the strongest CO adsorption ability,and in-situ Fourier-transform infrared spectroscopy(FTIR)showed the strongest*COCO and*CO signals for the Cu NNs.These experimental results demonstrate that high-curvature nanoneedles can induce a large local electric field,thus promoting C-C coupling.As a result,the Cu NNs show a maximum FEC_(2)of 44%for CO_(2)RR at a low potential(-0.6 V vs.RHE),which is approximately 2.2 times that of the Cu NPs.This work provides an effective strategy for enhancing the production of multi-carbon products during CO_(2)RR.展开更多
A series of Na-W-Mn-Zr/SiO2 catalysts promoted by different contents of S or/and P were prepared and their catalytic performance for oxidative coupling of methane was investigated to clarify the effect of S and P on t...A series of Na-W-Mn-Zr/SiO2 catalysts promoted by different contents of S or/and P were prepared and their catalytic performance for oxidative coupling of methane was investigated to clarify the effect of S and P on the Na-W-Mn-Zr/SiO2 catalyst. The catalysts were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). From the characterization results, it is found that the addition of S and P to the Na-W-Mn-ZffSiO2 catalyst helps the formation of active phases, such as α-cristobalite, Na2WO4, ZrO2, and Na2SO4. Moreover, the addition of S and P increases the concentration of surface-active oxygen species by improving the migration of active components from the bulk phase to the surface of the catalyst. According to the activity test, impressive methane conversion and C2 hydrocarbons yield were obtained at a low temperature of 1023 K over the six-component Na-W-Mn-Zr-S-P/SiO2 catalyst, which contained 2 wt% S and 0.4 wt% P simultaneously. The deactivation of Na-W-Mn-Zr-S-P/SiO2 was due to the loss of surface active components.展开更多
A series of Ce-promoted Mn-Na2WO4/SiO2 catalysts were prepared by incipient wetness impregnation method, and their catalytic performance for oxidative coupling of methane (OCM) was investigated at atmospheric pressu...A series of Ce-promoted Mn-Na2WO4/SiO2 catalysts were prepared by incipient wetness impregnation method, and their catalytic performance for oxidative coupling of methane (OCM) was investigated at atmospheric pressure in a micro-quartz-tube reactor. The catalysts were characterized by X-ray diffraction (XRD), temperature program reduction (TPR) and BET surface area. Ce promoter increased surface area and Na2WO4 species dispersion, which enriched the amount of the surface species. In addition, Ce promoter increased the Na/W species reduction, but the reduction peak shifted to higher temperature. Stability test of 5wt%Ce catalyst indicated suitable performance and stability. The selectivity and yield of C^2+ hydrocarbons after 50 h operation reached 65.5% and 19.6%, respectively, at 840 ℃ over 5wt%Ce-2wt%Mn5wt%Na2WO4/SiO2 catalyst.展开更多
The fixing of a silane coupling agent to Zn-Ni-silica(SiO_(2))composite coatings was studied for the purpose of developing a coating process as an alternative to chromating.The corrosion resistance of Zn-Ni-silica com...The fixing of a silane coupling agent to Zn-Ni-silica(SiO_(2))composite coatings was studied for the purpose of developing a coating process as an alternative to chromating.The corrosion resistance of Zn-Ni-silica composite coatings was rem arkably improved by the silica nanoparticles in the composite,which were disper sed in the surface of this film.The silane coupling agent formed chemical bonds with the inorganic silica particles during the silane coupling treatment on the se composite coatings.The treatment suppressed the formation of white corrosion products to the same extent as chromating,as measured in salt spray tests.It is concluded that treating Zn-Ni-silica composite coatings with silane coupling agents is a viable alternative technique to chromating.展开更多
The catalyst screening tests for carbon dioxide oxidative coupling of methane (CO2-OCM) have been investigated over ternary and binary metal oxide catalysts. The catalysts are prepared by doping MgO- and CeO2-based so...The catalyst screening tests for carbon dioxide oxidative coupling of methane (CO2-OCM) have been investigated over ternary and binary metal oxide catalysts. The catalysts are prepared by doping MgO- and CeO2-based solids with oxides from alkali (Li2O), alkaline earth (CaO), and transition metal groups (WO3 or MnO). The presence of the peroxide (O2-2) active sites on the Li2O2, revealed by Raman spectroscopy, may be the key factor in the enhanced performance of some of the Li2O/MgO catalysts. The high reducibility of the CeO2 catalyst, an important factor in the CO2-OCM catalyst activity, may be enhanced by the presence of manganese oxide species. The manganese oxide species increases oxygen mobility and oxygen vacancies in the CeO2 catalyst. Raman and Fourier Transform Infra Red (FT-IR) spectroscopies revealed the presence of lattice vibrations of metal-oxygen bondings and active sites in which the peaks corresponding to the bulk crystalline structures of Li2O, CaO, WO3 and MnO are detected. The performance of 5%MnO/15%CaO/CeO2 catalyst is the most potential among the CeO2-based catalysts, although lower than the 2%Li2O/MgO catalyst. The 2%Li2O/MgO catalyst showed the most promising C2+ hydrocarbons selectivity and yield at 98.0% and 5.7%, respectively.展开更多
Urea is widely used as fertilizer and is a key substance supporting global food production. However, the traditional industrial synthesis of urea faces the challenges with high energy consumption and serious environme...Urea is widely used as fertilizer and is a key substance supporting global food production. However, the traditional industrial synthesis of urea faces the challenges with high energy consumption and serious environmental problems. With the increasing global demand for environmental protection and sustainable development, it is much necessary to develop novel and clean methods for the synthesis of urea.Electrocatalysis provides an efficient and renewable synthesis route that can directly produce urea at room temperature and atmospheric pressure by the coupling of CO_(2) and nitrogenous molecules. In this review, we summarized the most recent advances in electrochemical synthesis of urea via CAN coupling systematically, focusing on the coupling of CO_(2) and different nitrogen sources. And the associated coupling mechanism, catalysts optimization, and electrolyzer design are well discussed. Moreover, the challenges and future directions for electrocatalytic CAN coupling are prospected. This review will provide timely and valuable guidance for others and attract more interests to promote the development of electrochemical synthesis of urea or other valuable chemicals containing CAN bond.展开更多
The atmospheric carbon dioxide(CO_(2))concentration has been increasing rapidly since the Industrial Revolution,which has led to unequivocal global warming and crucial environmental change.It is extremely important to...The atmospheric carbon dioxide(CO_(2))concentration has been increasing rapidly since the Industrial Revolution,which has led to unequivocal global warming and crucial environmental change.It is extremely important to investigate the interactions among atmospheric CO_(2),the physical climate system,and the carbon cycle of the underlying surface for a better understanding of the Earth system.Earth system models are widely used to investigate these interactions via coupled carbon-climate simulations.The Chinese Academy of Sciences Earth System Model version 2(CAS-ESM2.0)has successfully fixed a two-way coupling of atmospheric CO_(2)with the climate and carbon cycle on land and in the ocean.Using CAS-ESM2.0,we conducted a coupled carbon-climate simulation by following the CMIP6 proposal of a historical emissions-driven experiment.This paper examines the modeled CO_(2)by comparison with observed CO_(2)at the sites of Mauna Loa and Barrow,and the Greenhouse Gases Observing Satellite(GOSAT)CO_(2)product.The results showed that CAS-ESM2.0 agrees very well with observations in reproducing the increasing trend of annual CO_(2)during the period 1850-2014,and in capturing the seasonal cycle of CO_(2)at the two baseline sites,as well as over northern high latitudes.These agreements illustrate a good ability of CAS-ESM2.0 in simulating carbon-climate interactions,even though uncertainties remain in the processes involved.This paper reports an important stage of the development of CAS-ESM with the coupling of carbon and climate,which will provide significant scientific support for climate research and China’s goal of carbon neutrality.展开更多
In this paper, the conversion of CO2/CH4 by using pulse corona plasma was studied at atmospheric pressure and ambient temperature. The effects of ratio of CO2/CH4, pulse voltage and repeated frequency of plasma discha...In this paper, the conversion of CO2/CH4 by using pulse corona plasma was studied at atmospheric pressure and ambient temperature. The effects of ratio of CO2/CH4, pulse voltage and repeated frequency of plasma discharge were first studied in the system.展开更多
The study of scale up for the oxidative coupling of methane (OCM) has been carried out in a 200 ml stainless steel fixed-bed reactor over a 5wt% Na2WO4-1.9wt% Mn/SiO2 (W-Mn/SiO2) catalyst. The effects of reaction ...The study of scale up for the oxidative coupling of methane (OCM) has been carried out in a 200 ml stainless steel fixed-bed reactor over a 5wt% Na2WO4-1.9wt% Mn/SiO2 (W-Mn/SiO2) catalyst. The effects of reaction conditions were investigated in detail. The results showed that, with increasing reaction temperature, the gas-phase reaction was enhanced and a significant amount of methane was converted into COx; with the CH4/O2 molar ratio of 5, the highest C2 (ethylene and ethane) yield of 25% was achieved; the presence of steam (as diluent) had a positive effect on the C2 selectivity and yield. Under lower methane gaseous hourly space velocity (GHSV), higher selectivity and yield of C2 were obtained as the result of the decrease of released heat energy. In 100 h reaction time, the C2 selectivity of 66%-61% and C2 yield of 24.2%-25.4% were achieved by a single pass without any significant loss in catalytic performance.展开更多
The performance of BaC12-TiO2-SnO2 composite catalysts in oxidative coupling of methane reaction has been investigated. A series of BaC12-TiO2, BaC1E-SnO2, TiO2-SnO2, and BaC12-TiO2-SnO2 catalysts were prepared, and c...The performance of BaC12-TiO2-SnO2 composite catalysts in oxidative coupling of methane reaction has been investigated. A series of BaC12-TiO2, BaC1E-SnO2, TiO2-SnO2, and BaC12-TiO2-SnO2 catalysts were prepared, and characterized by BET, XRD, XPS, CO2-TPD and H2-TPR, respectively. The synergistic effect among BaC12, SnO2 and TiO2 compositions enhances the catalytic performance. The best C2 selectivity and ethylene yield are obtained on the catalyst with the equal molar amount of the three compositions (BaC12 : TiO2 : SnO2 molar ratio of 1 : 1 : 1). The optimal reaction conditions are as follows: 800 ℃, 44 mL.min-1 for methane, 22 mL.min-1 for oxygen and a space velocity of 5000 mL-h-1 .g-1, and the C2H4 yield over the catalyst is 20.1% with the CH4 conversion of 43.8% and C2 selectivity of 53.3%.展开更多
Electrocatalytic reduction of CO_(2) converts intermittent renewable electricity into value-added liquid products with an enticing prospect,but its practical application is hampered due to the lack of high-performance...Electrocatalytic reduction of CO_(2) converts intermittent renewable electricity into value-added liquid products with an enticing prospect,but its practical application is hampered due to the lack of high-performance electrocatalysts.Herein,we elaborately design and develop strongly coupled nanosheets composed of Ag nanoparticles and Sn-SnO_(2) grains,designated as Ag/Sn-SnO_(2) nanosheets(NSs),which possess optimized electronic structure,high electrical conductivity,and more accessible sites.As a result,such a catalyst exhibits unprecedented catalytic performance toward CO_(2)-to-formate conversion with near-unity faradaic efficiency(≥90%),ultrahigh partial current density(2,000 mA cm^(−2)),and superior long-term stability(200 mA cm^(−2),200 h),surpassing the reported catalysts of CO_(2) electroreduction to formate.Additionally,in situ attenuated total reflection-infrared spectra combined with theoretical calculations revealed that electron-enriched Sn sites on Ag/Sn-SnO_(2)NSs not only promote the formation of*OCHO and alleviate the energy barriers of*OCHO to*HCOOH,but also impede the desorption of H*.Notably,the Ag/Sn-SnO_(2)NSs as the cathode in a membrane electrode assembly with porous solid electrolyte layer reactor can continuously produce~0.12 M pure HCOOH solution at 100 mA cm^(−2)over 200 h.This work may inspire further development of advanced electrocatalysts and innovative device systems for promoting practical application of producing liquid fuels from CO_(2).展开更多
In this work,the influence of CO2 on the structural variation and catalytic performance of Na2WO4/Mn/Si O2 for oxidative coupling of methane to ethylene was investigated. The catalyst was prepared by impregnation meth...In this work,the influence of CO2 on the structural variation and catalytic performance of Na2WO4/Mn/Si O2 for oxidative coupling of methane to ethylene was investigated. The catalyst was prepared by impregnation method and characterized by XRD,Raman and XPS techniques. Appropriate amount of CO2 in the reactant gases enhanced the formation of surface tetrahedral Na2WO4 species and promoted the migration of O in MOx,Na,W from the catalyst bulk to surface,which were favorable for oxidative coupling of methane. When the molar ratio of CH4/O2/CO2 was 3/1/2,enriched surface tetrahedral Na2WO4 species and high surface concentration of O in MOx,Na,W were detected,and then high CH4 conversion of 33.1% and high C2H4 selectivity of 56.2% were obtained. With further increase of CO2 in the reagent gases,the content of active surface tetrahedral Na2WO4 species and surface concentration of O in MOx,Na,W decreased,while that of inactive species(Mn WO4 and Mn2O3) increased dramatically,leading to low CH4 conversion and low C2H4 selectivity. It could be speculated that Na2WO4 crystal was transformed into Mn WO4 crystal with excessive CO2 added under the reaction conditions. Pretreatment of Na2WO4/Mn/Si O2 catalyst by moderate amount of CO2 before OCM also promoted the formation of Na2WO4 species.展开更多
A novel color image encryption scheme is developed to enhance the security of encryption without increasing the complexity. Firstly, the plain color image is decomposed into three grayscale plain images, which are con...A novel color image encryption scheme is developed to enhance the security of encryption without increasing the complexity. Firstly, the plain color image is decomposed into three grayscale plain images, which are converted into the frequency domain coefficient matrices(FDCM) with discrete cosine transform(DCT) operation. After that, a twodimensional(2D) coupled chaotic system is developed and used to generate one group of embedded matrices and another group of encryption matrices, respectively. The embedded matrices are integrated with the FDCM to fulfill the frequency domain encryption, and then the inverse DCT processing is implemented to recover the spatial domain signal. Eventually,under the function of the encryption matrices and the proposed diagonal scrambling algorithm, the final color ciphertext is obtained. The experimental results show that the proposed method can not only ensure efficient encryption but also satisfy various sizes of image encryption. Besides, it has better performance than other similar techniques in statistical feature analysis, such as key space, key sensitivity, anti-differential attack, information entropy, noise attack, etc.展开更多
Na-W-Mn-Zr-S-P/SiO2 catalysts for oxidative coupling of methane (OCM) were prepared by incipient wetness impregnation, sol-gel and mixture slurry methods. The catalyst prepared by mixture slurry method showed the be...Na-W-Mn-Zr-S-P/SiO2 catalysts for oxidative coupling of methane (OCM) were prepared by incipient wetness impregnation, sol-gel and mixture slurry methods. The catalyst prepared by mixture slurry method showed the best catalytic performance among all samples. In addition, the effects of different addition sequences of Na, W, Mn, Zr, S and P on the catalytic performance were studied. The absence of Na before the addition of Mn and Zr in the catalysts preparation depressed the formation of the active phases of Mn2O3 and ZrO2 and decreased the activities of the catalysts significantly.展开更多
Reaction chemistry of the OCM reaction on W-Mn/SiO_2 catalyst has beenreviewed in this account. Initial activity and selectivity, stability in a long-term reaction,reaction at elevated pressures and a modelling test i...Reaction chemistry of the OCM reaction on W-Mn/SiO_2 catalyst has beenreviewed in this account. Initial activity and selectivity, stability in a long-term reaction,reaction at elevated pressures and a modelling test in a stainless-steel fluidized-bed reactor showthat W-Mn/SiO_2 has promising performance for the development of an OCM process that directlyproduces ethylene from natural gas. A study on surface catalytic reaction kinetics and used catalyststructure characterization revealed a possible reason why C_2 and CO_x selectivity changed duringthe long-term reaction. Further improvement of the catalyst composition and preparation methodshould be a future direction of study on OCM reaction over W-Mn/SiO_2 catalyst.展开更多
基金support from the Tangshan Talent Funding Project(Grant No.A202202007)National Natural Science Foundation of China(Grant Nos.22102136 and 21703065)+2 种基金Natural Science Foundation of Hebei Province(Grant Nos.B2018209267 and E2022209039)Natural Science Foundation of Hubei Province(Grant No.2022CFB1001)Department of Education of Hubei Province(Grant No.Q20221701).
文摘Electrochemical C-C and C-N coupling reactions with the conversion of abundant and inexpensive small molecules,such as CO_(2) and nitrogencontaining species,are considered a promising route for increasing the value of CO_(2) reduction products.The development of high-performance catalysts is the key to the both electrocatalytic reactions.In this review,we present a systematic summary of the reaction systems for electrocatalytic CO_(2) reduction,along with the coupling mechanisms of C-C and C-N bonds over outstanding electrocatalytic materials recently developed.The key intermediate species and reaction pathways related to the coupling as well as the catalyst-structure relationship will be also discussed,aiming to provide insights and guidance for designing efficient CO_(2) reduction systems.
基金the National Natural Science Foundation of China(51303083)the National Natural Science Foundation of China for Excellent Young Scholars(51922050)+1 种基金the Natural Science Foundation of Jiangsu Province(BK20191293)the Fundamental Research Funds for the Central Universities(30920021123)。
文摘Photothermal catalytic CO_(2) conversion provides an effective solution targeting carbon neutrality by synergistic utilization of photon and heat.However,the C-C coupling initiated by photothermal catalysis is still a big challenge.Herein,a three-dimensional(3D)hierarchical W_(18)O_(49)/WTe_(2) hollow nanosphere is constructed through in-situ embodying of oxygen vacancy and tellurium on the scaffold of WO_(3).The light absorption towards near-infrared spectral region and CO_(2) adsorption are enhanced by the formation of half-metal WTe_(2) and the unique hierarchical hollow architecture.Combining with the generation of oxygen vacancy with strengthened CO_(2) capture,the photothermal effect on the samples can be sufficiently exploited for activating the CO_(2) molecules.In particular,the close contact between W_(18)O_(49)and WTe_(2) largely promotes the photoinduced charge separation and mass transfer,and thus the~*CHO intermediate formation and fixedness are facilitated.As a result,the C-C coupling can be evoked between tungsten and tellurium atoms on WTe_(2).The ethylene production by optimized W_(18)O_(49)/WTe_(2) reaches 147.6μmol g^(-1)with the selectivity of 80%.The in-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)and density functional theory(DFT)calculations are performed to unveil the presence and significance of aldehyde intermediate groups in C-C coupling.The half-metallic WTe_(2) cocatalyst proposes a new approach for efficient CO_(2) conversion with solar energy,and may especially create a new platform for the generation of multi-carbon products.
基金supported by the National Natural Science Foundation of China(52072196,52002200,52102106,52202262,22379081,22379080)the Major Basic Research Program of Natural Science Foundation of Shandong Province(ZR2020ZD09)+1 种基金the Natural Science Foundation of Shandong Province(ZR2020QE063,ZR202108180009,ZR2023QE059)the Project funded by China Postdoctoral Science Foundation(2023M741871)。
文摘Steering the directional carrier migration across the interface is a central mission for efficient photocatalytic reactions.In this work,an atomic-shared heterointerface is constructed between the defect-rich ZnIn_(2)S_(4)(HVs-ZIS)and CoIn_(2)S_(4)(CIS)via a defect-guided heteroepitaxial growth strategy.The strong interface coupling induces adequate carriers exchanging passageway between HVs-ZIS and CIS,enhancing the internal electric field(IEF)in the ZnIn_(2)S_(4)/CoIn_(2)S_(4)(HVs-ZIS/CIS)heterostructure.The defect structure in HVs-ZIS induces an additional defect level,improving the separation efficiency of photocarriers.Moreover,promoted by the IEF and intimate heterointerface,photogenerated electrons trapped by the defect level can migrate to the valence band of CIS,contributing to massive photogenerated electrons with intense reducibility in HVs-ZIS/CIS.Consequently,the HVs-ZIS/CIS heterostructure performs a boosted H_(2)evolution activity of 33.65 mmol g^(-1)h^(-1).This work highlights the synergistic effects of defect and strong interface coupling in regulating carrier transfer and paves a brave avenue for constructing efficient heterostructure photocatalysts.
基金supported by Natural Science Basic Research Program in Shaanxi Province of China(No.2023-JCYB-574)National Natural Science Foundation of China(No.62204203).
文摘High qualityβ-Ga_(2)O_(3)single crystal nanobelts with length of 2−3 mm and width from tens of microns to 132μm were synthesized by carbothermal reduction method.Based on the grown nanobelt with the length of 600μm,the dual-Schottky-junctions coupling device(DSCD)was fabricated.Due to the electrically floating Ga_(2)O_(3)nanobelt region coupling with the double Schottky-junctions,the current I_(S2)increases firstly and rapidly reaches into saturation as increase the voltage V_(S2).The saturation current is about 10 pA,which is two orders of magnitude lower than that of a single Schottky-junction.In the case of solar-blind ultraviolet(UV)light irradiation,the photogenerated electrons further aggravate the coupling physical mechanism in device.I_(S2)increases as the intensity of UV light increases.Under the UV light of 1820μW/cm^(2),I_(S2)quickly enters the saturation state.At V_(S2)=10 V,photo-to-dark current ratio(PDCR)of the device reaches more than 104,the external quantum efficiency(EQE)is 1.6×10^(3)%,and the detectivity(D*)is 7.5×10^(12)Jones.In addition,the device has a very short rise and decay times of 25−54 ms under different positive and negative bias.DSCD shows unique electrical and optical control characteristics,which will open a new way for the application of nanobelt-based devices.
基金supported by a grant from the Shanghai Health and Family Planning Commission,China(No.201440290)
文摘The elastic and functional coupling of heart and vessels makes the stroke work (SW) of the heart optimal. Speckle tracking imaging (STI) can evaluate the myocardial strain and function. We studied ventricular-vascular coupling in 80 diabetic patients with different systolic function using STI. The patients were divided into two groups according to ejection fraction (EF): the diabetes mel- litus with normal EF (DMN) group and the diabetes mellitus with abnormal EF (DMA) group. Forty-two volunteers served as control group. The relative wall thickness (RWT), left ventricular mass index (LVMI), stroke volume (SV), SW, rate-pressure product (RPP), systemic vascular resis- tance index (SVRI), left ventricular end-systolic elastance (Ees), effective arterial elasticity (Ea) and ventricular-vascular coupling index (VVI) were measured and calculated by conventional echocardi- ography. The longitudinal strain (LS) at basement (LSBA), papillary muscle (LSvM) and cardiac apex (LSAv) was assessed with STI. It was found: (A) compared with control group, in DMN and DMA groups, LSBA, LSvM and LSAp decreased, and they were lower in DMA group. (B) VVI, RPP and SVRI increased, and they were higher in DMN group; Ees decreased, and it was lower in DMA group. (C) LSBA, LSpM, and LSAv had negative correlation with VVI. LSAp, RWT, LVMI and SW were independent predictors for VVI. The area under the receiver operating characteristic (ROC) curves was used for identification of DMA and DMN with LSBA, LSpM, and LSAp, and the area under the ROC of LSAp was the largest. This study supports that myocardial LS could reflect the ventricu- lar-vascular coupling. Different segments had an order to “respond to” the state of the coupling, and the cardiac apex might be the earliest.
文摘Cu-based catalysts are the most promising candidates for electrochemical CO_(2)reduction(CO_(2)RR)to multi-carbon(C_(2))products.Optimizing the C-C coupling process,the rate-determining step for C_(2)product generation,is an important strategy to improve the production and selectivity of the C_(2)products.In this study,we determined that the local electric field can promote the C-C coupling reaction and enhance CO_(2)electroreduction to C_(2)products.First,finite-element simulations indicated that the high curvature of the Cu nanoneedles results in a large local electric field on their tips.Density functional theory(DFT)calculations proved that a large electric field can promote C-C coupling.Motivated by this prediction,we prepared a series of Cu catalysts with different curvatures.The Cu nanoneedles(NNs)exhibited the largest number of curvatures,followed by the Cu nanorods(NRs),and Cu nanoparticles(NPs).The Cu NNs contained the highest concentration of adsorbed K+,which resulted in the highest local electric field on the needles.CO adsorption sensor tests indicated that the Cu NNs exhibited the strongest CO adsorption ability,and in-situ Fourier-transform infrared spectroscopy(FTIR)showed the strongest*COCO and*CO signals for the Cu NNs.These experimental results demonstrate that high-curvature nanoneedles can induce a large local electric field,thus promoting C-C coupling.As a result,the Cu NNs show a maximum FEC_(2)of 44%for CO_(2)RR at a low potential(-0.6 V vs.RHE),which is approximately 2.2 times that of the Cu NPs.This work provides an effective strategy for enhancing the production of multi-carbon products during CO_(2)RR.
基金supported by the National Natural Science Foundation of China (20676116)
文摘A series of Na-W-Mn-Zr/SiO2 catalysts promoted by different contents of S or/and P were prepared and their catalytic performance for oxidative coupling of methane was investigated to clarify the effect of S and P on the Na-W-Mn-Zr/SiO2 catalyst. The catalysts were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). From the characterization results, it is found that the addition of S and P to the Na-W-Mn-ZffSiO2 catalyst helps the formation of active phases, such as α-cristobalite, Na2WO4, ZrO2, and Na2SO4. Moreover, the addition of S and P increases the concentration of surface-active oxygen species by improving the migration of active components from the bulk phase to the surface of the catalyst. According to the activity test, impressive methane conversion and C2 hydrocarbons yield were obtained at a low temperature of 1023 K over the six-component Na-W-Mn-Zr-S-P/SiO2 catalyst, which contained 2 wt% S and 0.4 wt% P simultaneously. The deactivation of Na-W-Mn-Zr-S-P/SiO2 was due to the loss of surface active components.
文摘A series of Ce-promoted Mn-Na2WO4/SiO2 catalysts were prepared by incipient wetness impregnation method, and their catalytic performance for oxidative coupling of methane (OCM) was investigated at atmospheric pressure in a micro-quartz-tube reactor. The catalysts were characterized by X-ray diffraction (XRD), temperature program reduction (TPR) and BET surface area. Ce promoter increased surface area and Na2WO4 species dispersion, which enriched the amount of the surface species. In addition, Ce promoter increased the Na/W species reduction, but the reduction peak shifted to higher temperature. Stability test of 5wt%Ce catalyst indicated suitable performance and stability. The selectivity and yield of C^2+ hydrocarbons after 50 h operation reached 65.5% and 19.6%, respectively, at 840 ℃ over 5wt%Ce-2wt%Mn5wt%Na2WO4/SiO2 catalyst.
文摘The fixing of a silane coupling agent to Zn-Ni-silica(SiO_(2))composite coatings was studied for the purpose of developing a coating process as an alternative to chromating.The corrosion resistance of Zn-Ni-silica composite coatings was rem arkably improved by the silica nanoparticles in the composite,which were disper sed in the surface of this film.The silane coupling agent formed chemical bonds with the inorganic silica particles during the silane coupling treatment on the se composite coatings.The treatment suppressed the formation of white corrosion products to the same extent as chromating,as measured in salt spray tests.It is concluded that treating Zn-Ni-silica composite coatings with silane coupling agents is a viable alternative technique to chromating.
文摘The catalyst screening tests for carbon dioxide oxidative coupling of methane (CO2-OCM) have been investigated over ternary and binary metal oxide catalysts. The catalysts are prepared by doping MgO- and CeO2-based solids with oxides from alkali (Li2O), alkaline earth (CaO), and transition metal groups (WO3 or MnO). The presence of the peroxide (O2-2) active sites on the Li2O2, revealed by Raman spectroscopy, may be the key factor in the enhanced performance of some of the Li2O/MgO catalysts. The high reducibility of the CeO2 catalyst, an important factor in the CO2-OCM catalyst activity, may be enhanced by the presence of manganese oxide species. The manganese oxide species increases oxygen mobility and oxygen vacancies in the CeO2 catalyst. Raman and Fourier Transform Infra Red (FT-IR) spectroscopies revealed the presence of lattice vibrations of metal-oxygen bondings and active sites in which the peaks corresponding to the bulk crystalline structures of Li2O, CaO, WO3 and MnO are detected. The performance of 5%MnO/15%CaO/CeO2 catalyst is the most potential among the CeO2-based catalysts, although lower than the 2%Li2O/MgO catalyst. The 2%Li2O/MgO catalyst showed the most promising C2+ hydrocarbons selectivity and yield at 98.0% and 5.7%, respectively.
基金National Natural Science Foundation of China (No. 22202065, 22075092 and U21A20500)。
文摘Urea is widely used as fertilizer and is a key substance supporting global food production. However, the traditional industrial synthesis of urea faces the challenges with high energy consumption and serious environmental problems. With the increasing global demand for environmental protection and sustainable development, it is much necessary to develop novel and clean methods for the synthesis of urea.Electrocatalysis provides an efficient and renewable synthesis route that can directly produce urea at room temperature and atmospheric pressure by the coupling of CO_(2) and nitrogenous molecules. In this review, we summarized the most recent advances in electrochemical synthesis of urea via CAN coupling systematically, focusing on the coupling of CO_(2) and different nitrogen sources. And the associated coupling mechanism, catalysts optimization, and electrolyzer design are well discussed. Moreover, the challenges and future directions for electrocatalytic CAN coupling are prospected. This review will provide timely and valuable guidance for others and attract more interests to promote the development of electrochemical synthesis of urea or other valuable chemicals containing CAN bond.
基金the National Key Research and Development Program of China(Grant No.2022YFE0106500)the Youth Innovation Promotion Association of the Chinese Academy of Sciences(Grant No.2022076)+1 种基金the National Key Scientific and Technological Infrastructure project“Earth System Numerical Simulation Facility”(EarthLab2023-EL-ZD-00012)。
文摘The atmospheric carbon dioxide(CO_(2))concentration has been increasing rapidly since the Industrial Revolution,which has led to unequivocal global warming and crucial environmental change.It is extremely important to investigate the interactions among atmospheric CO_(2),the physical climate system,and the carbon cycle of the underlying surface for a better understanding of the Earth system.Earth system models are widely used to investigate these interactions via coupled carbon-climate simulations.The Chinese Academy of Sciences Earth System Model version 2(CAS-ESM2.0)has successfully fixed a two-way coupling of atmospheric CO_(2)with the climate and carbon cycle on land and in the ocean.Using CAS-ESM2.0,we conducted a coupled carbon-climate simulation by following the CMIP6 proposal of a historical emissions-driven experiment.This paper examines the modeled CO_(2)by comparison with observed CO_(2)at the sites of Mauna Loa and Barrow,and the Greenhouse Gases Observing Satellite(GOSAT)CO_(2)product.The results showed that CAS-ESM2.0 agrees very well with observations in reproducing the increasing trend of annual CO_(2)during the period 1850-2014,and in capturing the seasonal cycle of CO_(2)at the two baseline sites,as well as over northern high latitudes.These agreements illustrate a good ability of CAS-ESM2.0 in simulating carbon-climate interactions,even though uncertainties remain in the processes involved.This paper reports an important stage of the development of CAS-ESM with the coupling of carbon and climate,which will provide significant scientific support for climate research and China’s goal of carbon neutrality.
文摘In this paper, the conversion of CO2/CH4 by using pulse corona plasma was studied at atmospheric pressure and ambient temperature. The effects of ratio of CO2/CH4, pulse voltage and repeated frequency of plasma discharge were first studied in the system.
文摘The study of scale up for the oxidative coupling of methane (OCM) has been carried out in a 200 ml stainless steel fixed-bed reactor over a 5wt% Na2WO4-1.9wt% Mn/SiO2 (W-Mn/SiO2) catalyst. The effects of reaction conditions were investigated in detail. The results showed that, with increasing reaction temperature, the gas-phase reaction was enhanced and a significant amount of methane was converted into COx; with the CH4/O2 molar ratio of 5, the highest C2 (ethylene and ethane) yield of 25% was achieved; the presence of steam (as diluent) had a positive effect on the C2 selectivity and yield. Under lower methane gaseous hourly space velocity (GHSV), higher selectivity and yield of C2 were obtained as the result of the decrease of released heat energy. In 100 h reaction time, the C2 selectivity of 66%-61% and C2 yield of 24.2%-25.4% were achieved by a single pass without any significant loss in catalytic performance.
文摘The performance of BaC12-TiO2-SnO2 composite catalysts in oxidative coupling of methane reaction has been investigated. A series of BaC12-TiO2, BaC1E-SnO2, TiO2-SnO2, and BaC12-TiO2-SnO2 catalysts were prepared, and characterized by BET, XRD, XPS, CO2-TPD and H2-TPR, respectively. The synergistic effect among BaC12, SnO2 and TiO2 compositions enhances the catalytic performance. The best C2 selectivity and ethylene yield are obtained on the catalyst with the equal molar amount of the three compositions (BaC12 : TiO2 : SnO2 molar ratio of 1 : 1 : 1). The optimal reaction conditions are as follows: 800 ℃, 44 mL.min-1 for methane, 22 mL.min-1 for oxygen and a space velocity of 5000 mL-h-1 .g-1, and the C2H4 yield over the catalyst is 20.1% with the CH4 conversion of 43.8% and C2 selectivity of 53.3%.
基金the National Science Fund for Distinguished Young Scholars(Grant No.52125103)the National Natural Science Foundation of China(Grant Nos.52301232,52071041,12074048,and 12147102)China Postdoctoral Science Foundation(Grant No.2022M720552).
文摘Electrocatalytic reduction of CO_(2) converts intermittent renewable electricity into value-added liquid products with an enticing prospect,but its practical application is hampered due to the lack of high-performance electrocatalysts.Herein,we elaborately design and develop strongly coupled nanosheets composed of Ag nanoparticles and Sn-SnO_(2) grains,designated as Ag/Sn-SnO_(2) nanosheets(NSs),which possess optimized electronic structure,high electrical conductivity,and more accessible sites.As a result,such a catalyst exhibits unprecedented catalytic performance toward CO_(2)-to-formate conversion with near-unity faradaic efficiency(≥90%),ultrahigh partial current density(2,000 mA cm^(−2)),and superior long-term stability(200 mA cm^(−2),200 h),surpassing the reported catalysts of CO_(2) electroreduction to formate.Additionally,in situ attenuated total reflection-infrared spectra combined with theoretical calculations revealed that electron-enriched Sn sites on Ag/Sn-SnO_(2)NSs not only promote the formation of*OCHO and alleviate the energy barriers of*OCHO to*HCOOH,but also impede the desorption of H*.Notably,the Ag/Sn-SnO_(2)NSs as the cathode in a membrane electrode assembly with porous solid electrolyte layer reactor can continuously produce~0.12 M pure HCOOH solution at 100 mA cm^(−2)over 200 h.This work may inspire further development of advanced electrocatalysts and innovative device systems for promoting practical application of producing liquid fuels from CO_(2).
基金support from the Ministry of Science and Technology (Nos.2012BAC20B10)the National Natural Science Foundation of China (Nos. 21321061 and 20976109)
文摘In this work,the influence of CO2 on the structural variation and catalytic performance of Na2WO4/Mn/Si O2 for oxidative coupling of methane to ethylene was investigated. The catalyst was prepared by impregnation method and characterized by XRD,Raman and XPS techniques. Appropriate amount of CO2 in the reactant gases enhanced the formation of surface tetrahedral Na2WO4 species and promoted the migration of O in MOx,Na,W from the catalyst bulk to surface,which were favorable for oxidative coupling of methane. When the molar ratio of CH4/O2/CO2 was 3/1/2,enriched surface tetrahedral Na2WO4 species and high surface concentration of O in MOx,Na,W were detected,and then high CH4 conversion of 33.1% and high C2H4 selectivity of 56.2% were obtained. With further increase of CO2 in the reagent gases,the content of active surface tetrahedral Na2WO4 species and surface concentration of O in MOx,Na,W decreased,while that of inactive species(Mn WO4 and Mn2O3) increased dramatically,leading to low CH4 conversion and low C2H4 selectivity. It could be speculated that Na2WO4 crystal was transformed into Mn WO4 crystal with excessive CO2 added under the reaction conditions. Pretreatment of Na2WO4/Mn/Si O2 catalyst by moderate amount of CO2 before OCM also promoted the formation of Na2WO4 species.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.62105004 and 52174141)the College Student Innovation and Entrepreneurship Fund Project(Grant No.202210361053)+1 种基金Anhui Mining Machinery and Electrical Equipment Coordination Innovation Center,Anhui University of Science&Technology(Grant No.KSJD202304)the Anhui Province Digital Agricultural Engineering Technology Research Center Open Project(Grant No.AHSZNYGC-ZXKF021)。
文摘A novel color image encryption scheme is developed to enhance the security of encryption without increasing the complexity. Firstly, the plain color image is decomposed into three grayscale plain images, which are converted into the frequency domain coefficient matrices(FDCM) with discrete cosine transform(DCT) operation. After that, a twodimensional(2D) coupled chaotic system is developed and used to generate one group of embedded matrices and another group of encryption matrices, respectively. The embedded matrices are integrated with the FDCM to fulfill the frequency domain encryption, and then the inverse DCT processing is implemented to recover the spatial domain signal. Eventually,under the function of the encryption matrices and the proposed diagonal scrambling algorithm, the final color ciphertext is obtained. The experimental results show that the proposed method can not only ensure efficient encryption but also satisfy various sizes of image encryption. Besides, it has better performance than other similar techniques in statistical feature analysis, such as key space, key sensitivity, anti-differential attack, information entropy, noise attack, etc.
基金supported by the financial support from National Natural Science Foundation of China (20676116)
文摘Na-W-Mn-Zr-S-P/SiO2 catalysts for oxidative coupling of methane (OCM) were prepared by incipient wetness impregnation, sol-gel and mixture slurry methods. The catalyst prepared by mixture slurry method showed the best catalytic performance among all samples. In addition, the effects of different addition sequences of Na, W, Mn, Zr, S and P on the catalytic performance were studied. The absence of Na before the addition of Mn and Zr in the catalysts preparation depressed the formation of the active phases of Mn2O3 and ZrO2 and decreased the activities of the catalysts significantly.
文摘Reaction chemistry of the OCM reaction on W-Mn/SiO_2 catalyst has beenreviewed in this account. Initial activity and selectivity, stability in a long-term reaction,reaction at elevated pressures and a modelling test in a stainless-steel fluidized-bed reactor showthat W-Mn/SiO_2 has promising performance for the development of an OCM process that directlyproduces ethylene from natural gas. A study on surface catalytic reaction kinetics and used catalyststructure characterization revealed a possible reason why C_2 and CO_x selectivity changed duringthe long-term reaction. Further improvement of the catalyst composition and preparation methodshould be a future direction of study on OCM reaction over W-Mn/SiO_2 catalyst.