The effect of Na-excess content in the precursor on the structural and electrochemical performances of sodium nickel manganese oxide(NNMO)prepared by sol-gel and electrospinning methods is investigated in this paper.X...The effect of Na-excess content in the precursor on the structural and electrochemical performances of sodium nickel manganese oxide(NNMO)prepared by sol-gel and electrospinning methods is investigated in this paper.X-ray diffraction results of the prepared NNMO without adding Na-excess content indicate sodium loss,while the mixed phase of P2/O′3-type layered NNMO presented after adding Na-excess content.Compared with the sol-gel method,the secondary phase of NiO is more suppressed by using the electrospinning method,which is further confirmed by field emission scanning electron microscope images.N_(2) adsorption-desorption isotherms show no remarkably difference in specific surface areas between different preparation methods and Na-excess contents.The analysis of X-ray absorption near edge structure indicates that the oxidation states of Ni and Mn are+2 and+4,respectively.For the electrochemical properties,superior electrochemical performance is observed in the NNMO electrode with a low Na-excess content of 5wt%.The highest specific capacitance is 36.07 F·g^(-1)at0.1 A·g^(-1)in the NNMO electrode prepared by using the sol-gel method.By contrast,the NNMO electrode prepared using the electrospinning method with decreased Na-excess content shows excellent cycling stability of 100%after charge-discharge measurements for 300 cycles.Therefore,controlling the Na excess in the precursor together with the preparation method is important for improving the electrochemical performance of Na-based electrode materials in supercapacitors.展开更多
Immobilizing primary electroactive nanomaterials in porous carbon matrix is an effective approach for boosting the electrochemical performance of potassium-ion batteries (PIBs) because of the synergy among functional ...Immobilizing primary electroactive nanomaterials in porous carbon matrix is an effective approach for boosting the electrochemical performance of potassium-ion batteries (PIBs) because of the synergy among functional components. Herein, an integrated hybrid architecture composed of ultrathin Cu_(3)P nanoparticles (~20 nm) confined in porous carbon nanosheets (Cu_(3)P⊂NPCSs) as a new anode material for PIBs is synthesized through a rational self-designed self-templating strategy. Benefiting from the unique structural advantages including more active heterointerfacial sites, intimate and stable electrical contact, effectively relieved volume change, and rapid K^(+) ion migration, the Cu_(3)P⊂NPCSs indicate excellent potassium-storage performance involving high reversible capacity, exceptional rate capability, and cycling stability. Moreover, the strong adsorption of K^(+) ions and fast potassium-ion reaction kinetics in Cu_(3)P⊂NPCSs is verified by the theoretical calculation investigation. Noted, the intercalation mechanism of Cu_(3)P to store potassium ions is, for the first time, clearly confirmed during the electrochemical process by a series of advanced characterization techniques.展开更多
Transitional metal phosphides(TMPs)anode materials usually have large volume change and weak diffusion kinetics,leading to poor cycle stability.Combining TMPs with conductive carbon matrix has been widely used to boos...Transitional metal phosphides(TMPs)anode materials usually have large volume change and weak diffusion kinetics,leading to poor cycle stability.Combining TMPs with conductive carbon matrix has been widely used to boost sodium storage.However,it still needs to make efforts in the rational and facile design of nano/micro-structural TMPs/carbon hybrid anode material.Herein,a MOFs-derived strategy is developed to synthesize porous yolk–shell Mo P/Cu_(3)P@carbon microcages(Mo P/Cu_(3)P@C)through in situ and confined phosphidation reaction as a high-performance sodium-ion batteries anode.This yolk–shell structure can offer adequate internal space to buffer the large volume expansion,shorten diffusion distance,and create more active sites of Na+.Especially,the Cu nanoparticles generated from Cu_(3)P have remarkable electronic conductivity of 5.73107S m-1(the second most conductive metal)to benefit transporting electrons.And the introduction of Mo(Mo P has high theoretical capacity of 633 mA h g^(-1))can enhance the reversible capacity of the whole anode material.Therefore,these porous yolk–shell Mo P/Cu_(3)P@carbon microcages possess excellent reversible capacity of 307.8 mA h g^(-1)at 1.0 A g^(-1)and extraordinary cycle stability of 132.1 m A h g^(-1)at 5.0 A g^(-1)even after 6000 cycles.展开更多
Lithium-sulfur batteries(LSBs)can work at high temperatures,but they suffer from poor cycle life stability due to the“shuttle effect”of polysulfides.In this study,pollen-derived porous carbon/cuprous phosphide(PC/Cu...Lithium-sulfur batteries(LSBs)can work at high temperatures,but they suffer from poor cycle life stability due to the“shuttle effect”of polysulfides.In this study,pollen-derived porous carbon/cuprous phosphide(PC/Cu_(3)P)hybrids were rationally synthesized using a one-step carbonization method using pollen as the source material,acting as the sulfur host for LSBs.In the hybrid,polar Cu_(3)P can markedly inhibit the“shuttle effect”by regulating the adsorption ability toward polysulfides,as confirmed by theoretical calculations and experimental tests.As an example,the camellia pollen porous carbon(CPC)/Cu_(3)P/S electrode shows a high capacity of 1205.6 mAh g^(−1) at 0.1 C,an ultralow capacity decay rate of 0.038%per cycle after 1000 cycles at 1 C,and a rather high initial Coulombic efficiency of 98.5%.The CPC/Cu_(3)P LSBs can work well at high temperatures,having a high capacity of 545.9 mAh g^(−1) at 1 C even at 150℃.The strategy of the PC/Cu_(3)P hybrid proposed in this study is expected to be an ideal cathode for ultrastable high-temperature LSBs.We believe that this strategy is universal and worthy of in-depth development for the next generation energy storage devices.展开更多
Finely modulated light-induced charge separation and transfer is a central challenge to achieve efficient photocatalysis.Although progress has been made in this field,most of the previous research works focused on the...Finely modulated light-induced charge separation and transfer is a central challenge to achieve efficient photocatalysis.Although progress has been made in this field,most of the previous research works focused on the separation or migration of photogenerated carriers but did not build a bridge between the two.How to realize the strong driving and precise migration of carriers has become the focus of our work.We report an ingeniously designed ternary heterojunction.Taking NiFe-MOF as the“parent material”,the FeP_(4)/Ni_(x)P_(y)heterojunction is derived in situ while maintaining the frame structure through gas-solid reaction,and finally the Z-type electron transfer is realized.With Cu_(3)P anchoring spindle matrix,an electron transport tunnel is opened up in Cu_(3)P/FeP_(4)/Ni_(x)P_(y)ternary heterojunction under the action of p-n heterojunction built-in electric field driving and accurate energy band matching.The strong driving force of the built-in electric field provides an inexhaustible power for the transmission of electrons,and the fine series of electron transmission channels realizes the precise transmission of electrons.The above fine design makes the perfect fit between the built-in electric field and the electron transfer channel,which not only effectively improves the embarrassing situation of insufficient electron driving force of hydrogen evolution reaction in the previous research,but also makes up for the weakening of semi-conductor reduction ability caused by the construction of traditional p-n heterostructures.This research work provides a new idea for the construction of multiple heterostructures and the design of fine interface engineering in the future.展开更多
In order to investigate whether an air–water plasma jet is beneficial to improve the efficiency of inactivation, a series of experiments were done using a ring-needle plasma jet. The water content in the working gas...In order to investigate whether an air–water plasma jet is beneficial to improve the efficiency of inactivation, a series of experiments were done using a ring-needle plasma jet. The water content in the working gas（air） was accurately measured based on the Karl Fischer method. The effects of water on the production of OH（A;Σ;–X;Π;） and O（3p;P–3s;S） were also studied by optical emission spectroscopy. The results show that the water content is in the range of 2.53–9.58 mg l;, depending on the gas/water mixture ratio. The production of OH（A;Σ;–X;Π;） rises with the increase of water content, whereas the O（3p;P–3s;S） shows a declining tendency with higher water content. The sterilization experiments indicate that this air–water plasma jet inactivates the P. digitatum spores very effectively and its efficiency rises with the increase of the water content. It is possible that OH（A;Σ;–X;Π;） is a more effective species in inactivation than O（3p;P–3s;S） and the water content benefit the spore germination inhibition through rising the OH（A;Σ;–X;Π;） production. The maximum of the inactivation efficacy is up to 93% when the applied voltage is -6.75 kV and the water content is 9.58 mg l;.展开更多
Potassium-ions batteries(PIBs)are attracting increasing attention as up-and-coming youngster in largescale grid-level energy storage benefiting from its low-cost and high energy density.Nevertheless,enough researches ...Potassium-ions batteries(PIBs)are attracting increasing attention as up-and-coming youngster in largescale grid-level energy storage benefiting from its low-cost and high energy density.Nevertheless,enough researches regarding indispensable cathode materials for PIBs are badly absent.Herein,we synthesize K-deficient layered manganese-based oxides(P2-K_(0.21)MnO_(2) and P3-K_(0.23)MnO_(2))and investigate them as cathode of PIBs for the first time.As the newcomer of potassium-containing layered manganese-based oxides(K_(x)MnO_(2))group,P2-K_(0.21)MnO_(2) delivers high discharge capacity of 99.3 mAh g^(-1) and P3-K_(0.23)MnO_(2) exhibits remarkable capacity retention rate of 75.5%.Besides,in-situ XRD and ex-situ XRD measurements reveal the reversible phase transition of P2-K_(0.21)MnO_(2) and P3-K_(0.23)MnO_(2) with the potassium-ions extraction and reinsertion,respectively.This work contributes to a better understanding for the potassium storage in K-deficient layered K_(x)MnO_(2)(x≤0.23),possessing an important basic scientific significance for the exploitation and application of layered K_(x)MnO_(2) in PIBs.展开更多
Combining metal to form metal phosphide is a promising strategy to address the fast capacity decay of P rooted from its low electronic conductivity and large volume changes upon cycling. Cu_(3)P, which possesses a hig...Combining metal to form metal phosphide is a promising strategy to address the fast capacity decay of P rooted from its low electronic conductivity and large volume changes upon cycling. Cu_(3)P, which possesses a high theoretical gravimetric and volumetric capacity of 363 m Ahág^(-1) and 1028 AháL^(-1) and reasonable volume expansion of 156% during sodiation, was investigated as anode material in SIBs. Hollow-structured Cu_(3)P electrode delivers an initial de-sodiation capacity of * 159.0 m Ahág^(-1) with high capacity retention of ~85.1% over 50 cycles at 0.2 C rate and exhibits good rate performance,retaining 70% of the capacity when the current density increases from 0.2 C to 1.6 C. A 3 V-class full cell consisting of P2-Na_(2/3) Ni_(1/3) Mn_(1/2) Ti_(1/6)O_(2) cathode and Cu_(3)P anode was also assembled, which could achieve an energy density of ~189.3 Whákg^(-1)(based on the mass of both electrode materials) and average discharge voltage of~2.91 V when cycled in 1.0-4.3 V at 0.1C.展开更多
Ambient electroreduction of nitrogen(N_(2))is considered as a green and feasible approach for ammonia(NH_(3))synthesis,which urgently demands for efficient electrocatalyst.Morphology has close relationship with cataly...Ambient electroreduction of nitrogen(N_(2))is considered as a green and feasible approach for ammonia(NH_(3))synthesis,which urgently demands for efficient electrocatalyst.Morphology has close relationship with catalytic activity of heterogeneous catalysts.Nanoribbon is attractive nanostructure,which possesses the flexibility of one-dimensional nanomaterials,the large surface area of two-dimensional nanomaterials,and lateral size confinement effects.In this work,Cu_(3)P nanoribbon is proposed as a highly efficient electrocatalyst for N_(2)-to-NH_(3)conversion under benign conditions.When measured in N_(2)-saturated 0.1 M HCl,such Cu_(3)P nanoribbon achieves high performance with an excellent Faradaic efficiency as high as 37.8%and a large yield of 18.9μg·h^(−1)·mgcat.−1 at−0.2 V.It also demonstrates outstanding stability in long-term electrolysis test at least for 45 h.展开更多
Alkenols are important intermediates for the industrial manufacture of various commodities and fine chemicals.At present,alkenols are produced via thermocatalytic semihydrogenation of corresponding alkynols using prec...Alkenols are important intermediates for the industrial manufacture of various commodities and fine chemicals.At present,alkenols are produced via thermocatalytic semihydrogenation of corresponding alkynols using precious metal Pd-based catalysts in pressurized hydrogen atmosphere.In this work,we highlight an efficient electrocatalytic strategy for selectively reducing alkynols to alkenols under ambient conditions.Using 2-methyl-3-butyn-2-ol as a model alkynol,Cu3P nanoarrays anchored on Cu foam remarkably deliver an industrial-level partial current density of 0.79 A·cm^(-2) and a specific selectivity of 98%for 2-methyl-3-buten-2-ol in acidic solution.Over a 40-runs stability test,Cu3P nanoarrays maintain 90%alkynol conversion and 90%alkenol selectivity.Even in a large two-electrode flow electrolyser,the single-pass alkynol conversion and alkenol selectivity of Cu3P nanoarrays exceed 90%.Moreover,this selective electrocatalytic hydrogenation approach is broadly feasible for the production of various water-soluble alkenols.Electrochemical analyses,theoretical simulation and electrochemical in-situ infrared investigations together reveal that exothermic alkynol hydrogenation,facile alkenol desorption and formation of active H on Cu3P surfaces account for the excellent electrocatalytic performance.展开更多
基金financially supported by (i) Suranaree University of Technology,(ii) Thailand Science Research and Innovation,and (iii) National Science,Research and Innovation Fund(project codes 90464 and 160363)。
文摘The effect of Na-excess content in the precursor on the structural and electrochemical performances of sodium nickel manganese oxide(NNMO)prepared by sol-gel and electrospinning methods is investigated in this paper.X-ray diffraction results of the prepared NNMO without adding Na-excess content indicate sodium loss,while the mixed phase of P2/O′3-type layered NNMO presented after adding Na-excess content.Compared with the sol-gel method,the secondary phase of NiO is more suppressed by using the electrospinning method,which is further confirmed by field emission scanning electron microscope images.N_(2) adsorption-desorption isotherms show no remarkably difference in specific surface areas between different preparation methods and Na-excess contents.The analysis of X-ray absorption near edge structure indicates that the oxidation states of Ni and Mn are+2 and+4,respectively.For the electrochemical properties,superior electrochemical performance is observed in the NNMO electrode with a low Na-excess content of 5wt%.The highest specific capacitance is 36.07 F·g^(-1)at0.1 A·g^(-1)in the NNMO electrode prepared by using the sol-gel method.By contrast,the NNMO electrode prepared using the electrospinning method with decreased Na-excess content shows excellent cycling stability of 100%after charge-discharge measurements for 300 cycles.Therefore,controlling the Na excess in the precursor together with the preparation method is important for improving the electrochemical performance of Na-based electrode materials in supercapacitors.
基金the financial supports provided by the National Natural Science Foundation of China(Nos.21971145,21871164)the Taishan Scholar Project Foundation of Shandong Province(No.ts20190908)+1 种基金the Natural Science Foundation of Shandong Province(No.ZR2019MB024)the Young Scholars Program of Shandong University(No.2017WLJH15)。
文摘Immobilizing primary electroactive nanomaterials in porous carbon matrix is an effective approach for boosting the electrochemical performance of potassium-ion batteries (PIBs) because of the synergy among functional components. Herein, an integrated hybrid architecture composed of ultrathin Cu_(3)P nanoparticles (~20 nm) confined in porous carbon nanosheets (Cu_(3)P⊂NPCSs) as a new anode material for PIBs is synthesized through a rational self-designed self-templating strategy. Benefiting from the unique structural advantages including more active heterointerfacial sites, intimate and stable electrical contact, effectively relieved volume change, and rapid K^(+) ion migration, the Cu_(3)P⊂NPCSs indicate excellent potassium-storage performance involving high reversible capacity, exceptional rate capability, and cycling stability. Moreover, the strong adsorption of K^(+) ions and fast potassium-ion reaction kinetics in Cu_(3)P⊂NPCSs is verified by the theoretical calculation investigation. Noted, the intercalation mechanism of Cu_(3)P to store potassium ions is, for the first time, clearly confirmed during the electrochemical process by a series of advanced characterization techniques.
基金supported by the National Natural Science Foundation of China(no.21646012)China Postdoctoral Science Foundation(no.2016M600253,2017T100246)+1 种基金the State Key Laboratory of Urban Water Resource and Environment,Harbin Institute of Technology(no.2019DX13)the Fundamental Research Funds for the Central Universities(Grant No.HIT.NSRIF.201836)
文摘Transitional metal phosphides(TMPs)anode materials usually have large volume change and weak diffusion kinetics,leading to poor cycle stability.Combining TMPs with conductive carbon matrix has been widely used to boost sodium storage.However,it still needs to make efforts in the rational and facile design of nano/micro-structural TMPs/carbon hybrid anode material.Herein,a MOFs-derived strategy is developed to synthesize porous yolk–shell Mo P/Cu_(3)P@carbon microcages(Mo P/Cu_(3)P@C)through in situ and confined phosphidation reaction as a high-performance sodium-ion batteries anode.This yolk–shell structure can offer adequate internal space to buffer the large volume expansion,shorten diffusion distance,and create more active sites of Na+.Especially,the Cu nanoparticles generated from Cu_(3)P have remarkable electronic conductivity of 5.73107S m-1(the second most conductive metal)to benefit transporting electrons.And the introduction of Mo(Mo P has high theoretical capacity of 633 mA h g^(-1))can enhance the reversible capacity of the whole anode material.Therefore,these porous yolk–shell Mo P/Cu_(3)P@carbon microcages possess excellent reversible capacity of 307.8 mA h g^(-1)at 1.0 A g^(-1)and extraordinary cycle stability of 132.1 m A h g^(-1)at 5.0 A g^(-1)even after 6000 cycles.
基金supported by the Innovation Platform of Energy Storage Engineering and New Material in Zhejiang University(No.K19-534202-002)the National Natural Science Foundation of China(No.21978261)the Zhejiang Provincial Key Research and Development Program of China(No.2021C01030).
文摘Lithium-sulfur batteries(LSBs)can work at high temperatures,but they suffer from poor cycle life stability due to the“shuttle effect”of polysulfides.In this study,pollen-derived porous carbon/cuprous phosphide(PC/Cu_(3)P)hybrids were rationally synthesized using a one-step carbonization method using pollen as the source material,acting as the sulfur host for LSBs.In the hybrid,polar Cu_(3)P can markedly inhibit the“shuttle effect”by regulating the adsorption ability toward polysulfides,as confirmed by theoretical calculations and experimental tests.As an example,the camellia pollen porous carbon(CPC)/Cu_(3)P/S electrode shows a high capacity of 1205.6 mAh g^(−1) at 0.1 C,an ultralow capacity decay rate of 0.038%per cycle after 1000 cycles at 1 C,and a rather high initial Coulombic efficiency of 98.5%.The CPC/Cu_(3)P LSBs can work well at high temperatures,having a high capacity of 545.9 mAh g^(−1) at 1 C even at 150℃.The strategy of the PC/Cu_(3)P hybrid proposed in this study is expected to be an ideal cathode for ultrastable high-temperature LSBs.We believe that this strategy is universal and worthy of in-depth development for the next generation energy storage devices.
基金supported by the National Natural Science Foundation of China (Nos.22005117 and 52072146)。
文摘Finely modulated light-induced charge separation and transfer is a central challenge to achieve efficient photocatalysis.Although progress has been made in this field,most of the previous research works focused on the separation or migration of photogenerated carriers but did not build a bridge between the two.How to realize the strong driving and precise migration of carriers has become the focus of our work.We report an ingeniously designed ternary heterojunction.Taking NiFe-MOF as the“parent material”,the FeP_(4)/Ni_(x)P_(y)heterojunction is derived in situ while maintaining the frame structure through gas-solid reaction,and finally the Z-type electron transfer is realized.With Cu_(3)P anchoring spindle matrix,an electron transport tunnel is opened up in Cu_(3)P/FeP_(4)/Ni_(x)P_(y)ternary heterojunction under the action of p-n heterojunction built-in electric field driving and accurate energy band matching.The strong driving force of the built-in electric field provides an inexhaustible power for the transmission of electrons,and the fine series of electron transmission channels realizes the precise transmission of electrons.The above fine design makes the perfect fit between the built-in electric field and the electron transfer channel,which not only effectively improves the embarrassing situation of insufficient electron driving force of hydrogen evolution reaction in the previous research,but also makes up for the weakening of semi-conductor reduction ability caused by the construction of traditional p-n heterostructures.This research work provides a new idea for the construction of multiple heterostructures and the design of fine interface engineering in the future.
基金supported by National Natural Science Foundation of China (NSFC) under Grants No. 51407020National Key Technology Research and Development Program of the Ministry of Science and Technology of China under Grants No. 2014BAC13B05Visiting Scholarship of State Key Laboratory of Power Transmission Equipment & System Security and New Technology (Chongqing University) No. 2007DA10512716404
文摘In order to investigate whether an air–water plasma jet is beneficial to improve the efficiency of inactivation, a series of experiments were done using a ring-needle plasma jet. The water content in the working gas（air） was accurately measured based on the Karl Fischer method. The effects of water on the production of OH（A;Σ;–X;Π;） and O（3p;P–3s;S） were also studied by optical emission spectroscopy. The results show that the water content is in the range of 2.53–9.58 mg l;, depending on the gas/water mixture ratio. The production of OH（A;Σ;–X;Π;） rises with the increase of water content, whereas the O（3p;P–3s;S） shows a declining tendency with higher water content. The sterilization experiments indicate that this air–water plasma jet inactivates the P. digitatum spores very effectively and its efficiency rises with the increase of the water content. It is possible that OH（A;Σ;–X;Π;） is a more effective species in inactivation than O（3p;P–3s;S） and the water content benefit the spore germination inhibition through rising the OH（A;Σ;–X;Π;） production. The maximum of the inactivation efficacy is up to 93% when the applied voltage is -6.75 kV and the water content is 9.58 mg l;.
基金support from the Key Project of Guangdong Province Nature Science Foundation (No. 2017B030311013)the Scientific and Technological Plan of Guangdong Province, Guangzhou and Qingyuan City, China (Nos. 2019B090905005, 2019B090911004, 2017B020227009, 2019DZX008, 2019A004)+2 种基金the financial support from the National Key R&D Program of China (2018YFB1502600)the National Natural Science Foundation of China (No. 51922042 and 51872098)the Sino-Singapore International Joint Research Institute (SSIJRI), Guangzhou 510700, China.
文摘Potassium-ions batteries(PIBs)are attracting increasing attention as up-and-coming youngster in largescale grid-level energy storage benefiting from its low-cost and high energy density.Nevertheless,enough researches regarding indispensable cathode materials for PIBs are badly absent.Herein,we synthesize K-deficient layered manganese-based oxides(P2-K_(0.21)MnO_(2) and P3-K_(0.23)MnO_(2))and investigate them as cathode of PIBs for the first time.As the newcomer of potassium-containing layered manganese-based oxides(K_(x)MnO_(2))group,P2-K_(0.21)MnO_(2) delivers high discharge capacity of 99.3 mAh g^(-1) and P3-K_(0.23)MnO_(2) exhibits remarkable capacity retention rate of 75.5%.Besides,in-situ XRD and ex-situ XRD measurements reveal the reversible phase transition of P2-K_(0.21)MnO_(2) and P3-K_(0.23)MnO_(2) with the potassium-ions extraction and reinsertion,respectively.This work contributes to a better understanding for the potassium storage in K-deficient layered K_(x)MnO_(2)(x≤0.23),possessing an important basic scientific significance for the exploitation and application of layered K_(x)MnO_(2) in PIBs.
基金financially supported by the National Natural Science Foundation of China (No. 51678182)the Start-up Grant for Shenzhen Oversea High-Level Talents。
文摘Combining metal to form metal phosphide is a promising strategy to address the fast capacity decay of P rooted from its low electronic conductivity and large volume changes upon cycling. Cu_(3)P, which possesses a high theoretical gravimetric and volumetric capacity of 363 m Ahág^(-1) and 1028 AháL^(-1) and reasonable volume expansion of 156% during sodiation, was investigated as anode material in SIBs. Hollow-structured Cu_(3)P electrode delivers an initial de-sodiation capacity of * 159.0 m Ahág^(-1) with high capacity retention of ~85.1% over 50 cycles at 0.2 C rate and exhibits good rate performance,retaining 70% of the capacity when the current density increases from 0.2 C to 1.6 C. A 3 V-class full cell consisting of P2-Na_(2/3) Ni_(1/3) Mn_(1/2) Ti_(1/6)O_(2) cathode and Cu_(3)P anode was also assembled, which could achieve an energy density of ~189.3 Whákg^(-1)(based on the mass of both electrode materials) and average discharge voltage of~2.91 V when cycled in 1.0-4.3 V at 0.1C.
基金the National Natural Science Foundation of China(No.22072015)the Opening Fund of Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research(Hunan Normal University),Ministry of Education(No.2020-02)+2 种基金Young Elite Scientist Sponsorship Program by CAST(No.YESS20210226)the Youth Innovation Promotion Association of the Chinese Academy of Sciences(No.2020354)Deanship of Scientific Research at King Khalid University,Abha,Saudi Arabia for funding this work through the Research Group Program under No.RGP.2/79/43.
文摘Ambient electroreduction of nitrogen(N_(2))is considered as a green and feasible approach for ammonia(NH_(3))synthesis,which urgently demands for efficient electrocatalyst.Morphology has close relationship with catalytic activity of heterogeneous catalysts.Nanoribbon is attractive nanostructure,which possesses the flexibility of one-dimensional nanomaterials,the large surface area of two-dimensional nanomaterials,and lateral size confinement effects.In this work,Cu_(3)P nanoribbon is proposed as a highly efficient electrocatalyst for N_(2)-to-NH_(3)conversion under benign conditions.When measured in N_(2)-saturated 0.1 M HCl,such Cu_(3)P nanoribbon achieves high performance with an excellent Faradaic efficiency as high as 37.8%and a large yield of 18.9μg·h^(−1)·mgcat.−1 at−0.2 V.It also demonstrates outstanding stability in long-term electrolysis test at least for 45 h.
基金financially supported by the National Natural Science Foundation of China(22005245 and 22201232)the Key Research and Development Program of Shaanxi Province(2023-YBGY-284)+3 种基金the Fundamental Research Funds for the Central Universities(G2022KY0606 and G2022KY05114)the Synergy Innovation Foundation of the University and Enterprise for Graduate Students in Northwestern Polytechnical University(CX2021037 and CX2022074)the Fundamental Research Funds for China Postdoctoral Science Foundation(BX2021247 and 2021M692635)the Natural Science Foundation of Shaanxi Province(2022JQ-083).
文摘Alkenols are important intermediates for the industrial manufacture of various commodities and fine chemicals.At present,alkenols are produced via thermocatalytic semihydrogenation of corresponding alkynols using precious metal Pd-based catalysts in pressurized hydrogen atmosphere.In this work,we highlight an efficient electrocatalytic strategy for selectively reducing alkynols to alkenols under ambient conditions.Using 2-methyl-3-butyn-2-ol as a model alkynol,Cu3P nanoarrays anchored on Cu foam remarkably deliver an industrial-level partial current density of 0.79 A·cm^(-2) and a specific selectivity of 98%for 2-methyl-3-buten-2-ol in acidic solution.Over a 40-runs stability test,Cu3P nanoarrays maintain 90%alkynol conversion and 90%alkenol selectivity.Even in a large two-electrode flow electrolyser,the single-pass alkynol conversion and alkenol selectivity of Cu3P nanoarrays exceed 90%.Moreover,this selective electrocatalytic hydrogenation approach is broadly feasible for the production of various water-soluble alkenols.Electrochemical analyses,theoretical simulation and electrochemical in-situ infrared investigations together reveal that exothermic alkynol hydrogenation,facile alkenol desorption and formation of active H on Cu3P surfaces account for the excellent electrocatalytic performance.
