2D MXenes are highly attractive for fabricating high-precision gas sensors operated at room temperature(RT)due to their high surface-to-volume ratio.However,the limited selectivity and low sensitivity are still long-s...2D MXenes are highly attractive for fabricating high-precision gas sensors operated at room temperature(RT)due to their high surface-to-volume ratio.However,the limited selectivity and low sensitivity are still long-standing challenges for their further applications.Herein,the self-assembly of 0D-2D heterostructure for highly sensitive NO_(2) detection was achieved by integrating ZnO nanoparticles on Ti_(3)C_(2)Tx MXene-derived TiO_(2) nanosheets(designated as ZnO@MTiO_(2)).ZnO nanoparticles can not only act as spacers to prevent the restacking of MTiO_(2) nanosheets and ensure effective transfer for gas molecules,but also enhance the sensitivity of the sensor the through trapping effect on electrons.Meanwhile,MTiO_(2) nanosheets facilitate gas diffusion for rapid sensor response.Benefiting from the synergistic effect of individual components,the ZnO@MTiO_(2)0D-2D heterostructure-based sensors revealed remarkable sensitivity and excellent selectivity to low concentration NO_(2) at RT.This work may facilitate the sensing application of MXene derivative and provide a new avenue for the development of high-performance gas sensors in safety assurance and environmental monitoring.展开更多
To overcome the serious technological issues affecting lithium-sulfur(Li-S) batteries,such as sluggish sulfur redox kinetics and the detrimental shuttle effect,heterostructure engineering has been investigated as a st...To overcome the serious technological issues affecting lithium-sulfur(Li-S) batteries,such as sluggish sulfur redox kinetics and the detrimental shuttle effect,heterostructure engineering has been investigated as a strategy to effectively capture soluble lithium polysulfide intermediates and promote their conversion reaction by integrating highly polar metal oxides with catalytically active metals sulfides.However,to fully exploit the outstanding properties of heterostructure-based composites,their detailed structure and interfacial contacts should be designed rationally.Herein,optimally arranged TiO_(2)and MoS_(2)-based heterostructures(TiO_(2)@MoS_(2)) are fabricated on carbon cloth as a multifunctional interlayer to efficiently trap polysulfide intermediates and accelerate their redox kinetics.Owing to the synergistic effects between TiO_(2)and MoS_(2)and the uniform heterointerface distribution that induces the ideally oriented built-in electric field,Li-S batteries with TiO_(2)@MoS_(2)interlayers exhibit high rate capability(601 mA h g^(-1)at 5 C),good cycling stability(capacity-fade rate of 0.067% per cycle over 500 cycles at2 C),and satisfactory areal capacity(5.2 mA h cm^(-2)) under an increased sulfur loading of 5.2 mg cm^(-2).Moreover,by comparing with a MoS_(2)@TiO_(2)interlayer composed of reversely arranged heterostructures,the effect of the built-in electric field’s direction on the electrocatalytic reactions of polysulfide intermediates is thoroughly investigated for the first time.The superior electrocatalytic activities of the rationally arranged TiO_(2)@MoS_(2)interlayer demonstrate the importance of optimizing the built-in electric field of heterostructures for producing high-performance Li-S batteries.展开更多
Constructing the hetrostructure is a feasible strategy to enhance the performances of photocatalysts. However, there are still some fundamental details and mechanisms for the specific design of photocatalysts with het...Constructing the hetrostructure is a feasible strategy to enhance the performances of photocatalysts. However, there are still some fundamental details and mechanisms for the specific design of photocatalysts with heterostructure,which need further confirming and explain.In this work,g-C_(3)N_(4)-based heterostructures are constructed with TiO_(2) in different ways,and their intrinsic factors to improve the photocatalytic activity are systematically studied by density functional theory(DFT).When g-C_(3)N_(4) combines horizontally with TiO_(2) to form a heterostructure,the interaction between them is dominated by van der Waals interaction.Although the recombination of photo-generated electron-hole pair cannot be inhibited significantly,this van der Waals interaction can regulate the electronic structures of the two components,which is conducive to the participation of photo-generated electrons and holes in the photocatalytic reaction.When the g-C_(3)N_(4) combines vertically with TiO_(2) to form a heterostructure,their interface states show obvious covalent features,which is very beneficial for the photo-generated electrons’ and holes’ transport along the opposite directions on both sides of the interface.Furthermore,the built-in electric field of g-C_(3)N_(4)/TiO_(2) heterostructure is directed from TiO_(2) layer to g-C_(3)N_(4) layer under equilibrium,so the photo-generated electron-hole pairs can be spatially separated from each other.These calculated results show that no matter how g-C_(3)N_(4) and TiO_(2) are combined together,the g-C_(3)N_(4)/TiO_(2) heterostructure can enhance the photocatalytic performance through corresponding ways.展开更多
The Cu2S/tetrapod-like ZnO whisker（T-ZnOw） heterostructures were successfully synthesized via a simple polyol process employing the poly（vinyl pyrrolidone）（PVP） as a surfactant.The as-prepared heterostructures w...The Cu2S/tetrapod-like ZnO whisker（T-ZnOw） heterostructures were successfully synthesized via a simple polyol process employing the poly（vinyl pyrrolidone）（PVP） as a surfactant.The as-prepared heterostructures were characterized by X-ray diffraction（XRD）,field emission scanning electron microscopy（FESEM）,X-ray photoelectron spectroscopy（XPS） and Fourier transform infrared（FTIR）.The photocatalytic properties of Cu2S/T-ZnOw nanocomposites synthesized with different PVP concentrations were evaluated by photodegradation of methyl orange（MO） under UV irradiation.The results show that the Cu2S/T-ZnOw nanocomposites exhibit remarkable improved photocatalytic property compared with the pure T-ZnOw.The sample prepared with 3.0 g/L PVP shows an excellent photocatalytic property and the highest photodegradation rate of MO is 97% after UV irradiation for 120 min.Besides,the photocatalytic activity of the photocatalyst has no evident decrease even after four cycles,which demonstrates that the Cu2S/T-ZnOw photocatalyst exhibits an excellent photostability.Moreover,the photocatalytic mechanism of the Cu2S/T-ZnOw nanocomposites was also discussed.展开更多
Lithium-sulfur (Li-S) batteries are considered as one of the promising next-generation energy storage systems because of their high energy density. While the low utilization of sulfur and sluggish reaction kinetics wo...Lithium-sulfur (Li-S) batteries are considered as one of the promising next-generation energy storage systems because of their high energy density. While the low utilization of sulfur and sluggish reaction kinetics would lead to degradation of electrochemical performance and thus hinder the practical application of Li-S batteries. Herein, a double-shelled TiO_(2)-graphene heterostructure (H-TiO_(2)/rGO) with abundant oxygen vacancies (OVs) and highly exposed active plane as advanced host material in Li-S batteries is designed. This rational structure not only provides sufficient active sites and lower bandgap for lithium polysulfides (LiPSs), but also builds smooth adsorption-diffusion-conversion of LiPSs on catalyst, which greatly reduces interfacial energy barrier and promotes the utilization of sulfur through suppressing the devastating shuttling effect. Combining the synergetic merits of strong anchoring ability and catalyzing the of LiPSs, the electrode (S-TiO_(2)/rGO-1) exhibits superior rate performance and long lifespan (1000 cycles at 1C, 0.023% capacity loss per cycle) with high columbic efficiency. This work paves an alternative way to establish smooth adsorption-diffusion-conversion of polysulfides on catalyst in Li-S batteries and provides a new sight to understand catalyst design in energy storage devices.展开更多
The conventional p-n heterojunction photocatalysts suffer from the incompatibility between the interfacial charge transfer efficiency and the redox ability of charge carriers.To optimize the interfacial charge transfe...The conventional p-n heterojunction photocatalysts suffer from the incompatibility between the interfacial charge transfer efficiency and the redox ability of charge carriers.To optimize the interfacial charge transfer of the conventional BiOI/TiO_(2) p-n photocatalyst,we synthesized the BiOI/Bi/TiO_(2) ternary photocatalyst with sandwiched metallic bismuth(Bi~0)by the oxygen-vacancy assisted method.The DFT calculation and structural characterizations confirmed the reaction of the electron-rich oxygen vacancies in the 2D-TiO_(2) nanosheets(TiO_(2)-NS)with the adsorbed BiO~+species.This reaction broke the Bi-O bonds to form Bi^(0) nanoparticles in-situ at the interface but still maintained the p-n heterojunction well.The NO-TPD and XRD analyses for samples correlated the Bi~0 formation with the oxygen vacancy concentrations well.The sandwiched Bi~0 functioned as an electronic transfer mediator like that in the Z-scheme heterostructure.Comparing with 0.20 BiOI/TiO_(2)-NP(NP,Nanoparticles),0.20 BiOI/Bi/TiO_(2)-NS-a(NS,Nanosheet)showed a much improved catalytic performance,i.e.,duplicated apparent quantum yield(AQY)and triplicated reaction rate constant(k).Also,the formation mechanism and the reaction mechanism were investigated in detail.This work provides a new strategy for the improving of the conventional p-n photocatalysts and new insights into the nature of the photocatalysis.展开更多
面向国家绿色低碳战略目标,变革化石资源合成氨技术路线变得尤为迫切,开发可再生能源制“绿氨”将成为合成氨领域未来的重要发展方向.将工业废水中的硝酸根(NO_(3)-)电催化还原为氨(NO_(3)RR),既可有效回收氨,又能消除硝酸根污染影响.然...面向国家绿色低碳战略目标,变革化石资源合成氨技术路线变得尤为迫切,开发可再生能源制“绿氨”将成为合成氨领域未来的重要发展方向.将工业废水中的硝酸根(NO_(3)-)电催化还原为氨(NO_(3)RR),既可有效回收氨,又能消除硝酸根污染影响.然而,NO_(3)RR涉及缓慢的八电子转移过程,含有多种反应中间体,其反应机理复杂不明.此外,水系电解液中存在的析氢竞争反应也为高效NO_(3)RR催化剂的开发设计带来了巨大的挑战.为突破高效催化剂的发展瓶颈,本文通过理论模拟,在低成本的催化剂上设计了高效的NO_(3)RR催化活性位点,并利用简单的制备策略合成了目标催化剂.同时,结合原位表征技术,阐明了NO_(3)RR的反应路径及催化机理.本文通过密度泛函理论(DFT)计算发现,Cu/TiO_(2)催化剂上的Cu-O-Ti-O_(v)结构具有较好的NO_(3)-还原活性,该结构不仅能够促进反应中间体NOx-的吸附和活化,还能有效抑制竞争析氢反应,从而降低NO_(3)RR的反应能垒.在该结构上,NO_(3)RR的反应路径为:NO_(3)^(*)→NO_(2)^(*)→HONO^(*)→NO^(*)→*NOH→*N→^(*)NH→*NH2→*NH_(3)→NH_(3).基于理论计算结果,分别采用浸渍法和尿素水解法制备了系列富含Cu-O-Ti-O_(v)结构的Cu/TiO_(2)催化剂.氮气等温吸附-脱附曲线、拉曼光谱(Raman)、电子顺磁共振波谱、X射线光电子能谱(XPS)和傅立叶红外光谱等结果发现,相比于采用浸渍法制备的系列Cu/TiO_(2)催化剂,采用尿素水解法制备的Cu/TiO_(2)(CT-U)催化剂具有更大的比表面积以及更多的Cu-O-Ti-O_(v)位点,说明尿素水解法可提高Cu颗粒在TiO_(2)载体表面的分散度,增强Cu颗粒与TiO_(2)载体之间的相互作用,提高Cu/TiO_(2)催化剂表面的Cu-O-Ti-O_(v)位点含量.将以上制备出的催化剂应用于催化NO_(3)RR中,结果表明,在-1.0 V vs.RHE还原电位下,CT-U催化剂上氨产率可达3046.5μg h^(-1) mgcat^(-1),高于大多数文献报道结果.循环稳定性测试结果表明,在Cu/TiO_(2)催化剂上构建Cu-O-Ti-O_(v)位点还能显著抑制电催化反应过程中Cu物种从Cu/TiO_(2)催化剂上溶出,从而显著增强催化剂的稳定性.此外,设计制备了不含氧空位的Cu/TiO_(2),TiO_(2)-x,Cu,Cu_(2)O以及CuO催化剂,并将其用于催化NO_(3)RR.结果发现,上述催化剂上的氨产率皆明显低于CT-U催化剂,说明Cu,Ti以及O_(v)构成的Cu-O-Ti-O_(v)结构具有较好的催化协同作用,从而显著提升了NO_(3)RR反应活性.最后,通过原位Raman及原位XPS表征检测反应中间体,验证了由DFT模拟出的NO_(3)RR反应路径.综上,通过在Cu/TiO_(2)催化剂上理论指导构建Cu-O-Ti-O_(v)活性位点,实现了NO_(3)RR性能的有效提升.Cu-O-Ti-O_(v)结构中的多位点协同作用不仅促进了NO_(x)-的吸附和活化,而且抑制了电催化过程中Cu物种从催化剂上的溶出,从而提高了催化剂的稳定性.本研究为设计高效稳定的NO_(3)RR催化剂提供了新思路.展开更多
基金supported by the National Natural Science Foundation of China(No.52103308)the Natural Science Foundation of Jiangsu Province of China(No.BK20210826)+4 种基金Outstanding Youth Foundation of Jiangsu Province of China(No.BK20211548)National Key Research and Development Program of China(No.2017YFE0115900)Innovative Science and Technology Platform Project of Cooperation between Yangzhou City and Yangzhou University(No.YZ2020266)Lvyang Jinfeng Plan for Excellent Doctor of Yangzhou City,Special Funds for Self-Made Experimental Equipment of Yangzhou Universitythe Doctor of Suzhou University Scientific Research Foundation Project(No.2022BSK003).
文摘2D MXenes are highly attractive for fabricating high-precision gas sensors operated at room temperature(RT)due to their high surface-to-volume ratio.However,the limited selectivity and low sensitivity are still long-standing challenges for their further applications.Herein,the self-assembly of 0D-2D heterostructure for highly sensitive NO_(2) detection was achieved by integrating ZnO nanoparticles on Ti_(3)C_(2)Tx MXene-derived TiO_(2) nanosheets(designated as ZnO@MTiO_(2)).ZnO nanoparticles can not only act as spacers to prevent the restacking of MTiO_(2) nanosheets and ensure effective transfer for gas molecules,but also enhance the sensitivity of the sensor the through trapping effect on electrons.Meanwhile,MTiO_(2) nanosheets facilitate gas diffusion for rapid sensor response.Benefiting from the synergistic effect of individual components,the ZnO@MTiO_(2)0D-2D heterostructure-based sensors revealed remarkable sensitivity and excellent selectivity to low concentration NO_(2) at RT.This work may facilitate the sensing application of MXene derivative and provide a new avenue for the development of high-performance gas sensors in safety assurance and environmental monitoring.
基金supported by the National R&D Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science and ICT (2018M3D1A1058793 and 2021R1A3B1068920)supported by the Creative Materials Discovery Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science and ICT (2018M3D1A1058744)the Yonsei Signature Research Cluster Program of 2021 (2021-22-0002)。
文摘To overcome the serious technological issues affecting lithium-sulfur(Li-S) batteries,such as sluggish sulfur redox kinetics and the detrimental shuttle effect,heterostructure engineering has been investigated as a strategy to effectively capture soluble lithium polysulfide intermediates and promote their conversion reaction by integrating highly polar metal oxides with catalytically active metals sulfides.However,to fully exploit the outstanding properties of heterostructure-based composites,their detailed structure and interfacial contacts should be designed rationally.Herein,optimally arranged TiO_(2)and MoS_(2)-based heterostructures(TiO_(2)@MoS_(2)) are fabricated on carbon cloth as a multifunctional interlayer to efficiently trap polysulfide intermediates and accelerate their redox kinetics.Owing to the synergistic effects between TiO_(2)and MoS_(2)and the uniform heterointerface distribution that induces the ideally oriented built-in electric field,Li-S batteries with TiO_(2)@MoS_(2)interlayers exhibit high rate capability(601 mA h g^(-1)at 5 C),good cycling stability(capacity-fade rate of 0.067% per cycle over 500 cycles at2 C),and satisfactory areal capacity(5.2 mA h cm^(-2)) under an increased sulfur loading of 5.2 mg cm^(-2).Moreover,by comparing with a MoS_(2)@TiO_(2)interlayer composed of reversely arranged heterostructures,the effect of the built-in electric field’s direction on the electrocatalytic reactions of polysulfide intermediates is thoroughly investigated for the first time.The superior electrocatalytic activities of the rationally arranged TiO_(2)@MoS_(2)interlayer demonstrate the importance of optimizing the built-in electric field of heterostructures for producing high-performance Li-S batteries.
基金Project supported by the National Natural Science Foundation of China(Grant No.11964015)。
文摘Constructing the hetrostructure is a feasible strategy to enhance the performances of photocatalysts. However, there are still some fundamental details and mechanisms for the specific design of photocatalysts with heterostructure,which need further confirming and explain.In this work,g-C_(3)N_(4)-based heterostructures are constructed with TiO_(2) in different ways,and their intrinsic factors to improve the photocatalytic activity are systematically studied by density functional theory(DFT).When g-C_(3)N_(4) combines horizontally with TiO_(2) to form a heterostructure,the interaction between them is dominated by van der Waals interaction.Although the recombination of photo-generated electron-hole pair cannot be inhibited significantly,this van der Waals interaction can regulate the electronic structures of the two components,which is conducive to the participation of photo-generated electrons and holes in the photocatalytic reaction.When the g-C_(3)N_(4) combines vertically with TiO_(2) to form a heterostructure,their interface states show obvious covalent features,which is very beneficial for the photo-generated electrons’ and holes’ transport along the opposite directions on both sides of the interface.Furthermore,the built-in electric field of g-C_(3)N_(4)/TiO_(2) heterostructure is directed from TiO_(2) layer to g-C_(3)N_(4) layer under equilibrium,so the photo-generated electron-hole pairs can be spatially separated from each other.These calculated results show that no matter how g-C_(3)N_(4) and TiO_(2) are combined together,the g-C_(3)N_(4)/TiO_(2) heterostructure can enhance the photocatalytic performance through corresponding ways.
基金Project (2009AA03Z427) supported by the High-tech Research and Development Program of ChinaProject (2006z02-006-3) supported by the Science Foundation of Sichuan Province,China
文摘The Cu2S/tetrapod-like ZnO whisker（T-ZnOw） heterostructures were successfully synthesized via a simple polyol process employing the poly（vinyl pyrrolidone）（PVP） as a surfactant.The as-prepared heterostructures were characterized by X-ray diffraction（XRD）,field emission scanning electron microscopy（FESEM）,X-ray photoelectron spectroscopy（XPS） and Fourier transform infrared（FTIR）.The photocatalytic properties of Cu2S/T-ZnOw nanocomposites synthesized with different PVP concentrations were evaluated by photodegradation of methyl orange（MO） under UV irradiation.The results show that the Cu2S/T-ZnOw nanocomposites exhibit remarkable improved photocatalytic property compared with the pure T-ZnOw.The sample prepared with 3.0 g/L PVP shows an excellent photocatalytic property and the highest photodegradation rate of MO is 97% after UV irradiation for 120 min.Besides,the photocatalytic activity of the photocatalyst has no evident decrease even after four cycles,which demonstrates that the Cu2S/T-ZnOw photocatalyst exhibits an excellent photostability.Moreover,the photocatalytic mechanism of the Cu2S/T-ZnOw nanocomposites was also discussed.
基金We acknowledge financially support from the National Natural Science Foundation of China(51272147)the Natural Science Foundation of Shaanxi Province(2015JM5208)the Graduate Innovation Found of Shaanxi University of Science and Technology.
文摘Lithium-sulfur (Li-S) batteries are considered as one of the promising next-generation energy storage systems because of their high energy density. While the low utilization of sulfur and sluggish reaction kinetics would lead to degradation of electrochemical performance and thus hinder the practical application of Li-S batteries. Herein, a double-shelled TiO_(2)-graphene heterostructure (H-TiO_(2)/rGO) with abundant oxygen vacancies (OVs) and highly exposed active plane as advanced host material in Li-S batteries is designed. This rational structure not only provides sufficient active sites and lower bandgap for lithium polysulfides (LiPSs), but also builds smooth adsorption-diffusion-conversion of LiPSs on catalyst, which greatly reduces interfacial energy barrier and promotes the utilization of sulfur through suppressing the devastating shuttling effect. Combining the synergetic merits of strong anchoring ability and catalyzing the of LiPSs, the electrode (S-TiO_(2)/rGO-1) exhibits superior rate performance and long lifespan (1000 cycles at 1C, 0.023% capacity loss per cycle) with high columbic efficiency. This work paves an alternative way to establish smooth adsorption-diffusion-conversion of polysulfides on catalyst in Li-S batteries and provides a new sight to understand catalyst design in energy storage devices.
基金financially supported by the National Natural Science Foundation of China(No.21043006 and 51702205)the Education Department of Guangdong Province(No.2018KTSCX063 and 2013KJCX0081)+2 种基金the Science and Technology Planning Project of Guangdong Province(No.2014A020216045)the 2020 Li Ka Shing Foundation Cross-Disciplinary Research Grant(2020LKSFG09A)the Guangdong Key Discipline Fund at GTIIT。
文摘The conventional p-n heterojunction photocatalysts suffer from the incompatibility between the interfacial charge transfer efficiency and the redox ability of charge carriers.To optimize the interfacial charge transfer of the conventional BiOI/TiO_(2) p-n photocatalyst,we synthesized the BiOI/Bi/TiO_(2) ternary photocatalyst with sandwiched metallic bismuth(Bi~0)by the oxygen-vacancy assisted method.The DFT calculation and structural characterizations confirmed the reaction of the electron-rich oxygen vacancies in the 2D-TiO_(2) nanosheets(TiO_(2)-NS)with the adsorbed BiO~+species.This reaction broke the Bi-O bonds to form Bi^(0) nanoparticles in-situ at the interface but still maintained the p-n heterojunction well.The NO-TPD and XRD analyses for samples correlated the Bi~0 formation with the oxygen vacancy concentrations well.The sandwiched Bi~0 functioned as an electronic transfer mediator like that in the Z-scheme heterostructure.Comparing with 0.20 BiOI/TiO_(2)-NP(NP,Nanoparticles),0.20 BiOI/Bi/TiO_(2)-NS-a(NS,Nanosheet)showed a much improved catalytic performance,i.e.,duplicated apparent quantum yield(AQY)and triplicated reaction rate constant(k).Also,the formation mechanism and the reaction mechanism were investigated in detail.This work provides a new strategy for the improving of the conventional p-n photocatalysts and new insights into the nature of the photocatalysis.
文摘面向国家绿色低碳战略目标,变革化石资源合成氨技术路线变得尤为迫切,开发可再生能源制“绿氨”将成为合成氨领域未来的重要发展方向.将工业废水中的硝酸根(NO_(3)-)电催化还原为氨(NO_(3)RR),既可有效回收氨,又能消除硝酸根污染影响.然而,NO_(3)RR涉及缓慢的八电子转移过程,含有多种反应中间体,其反应机理复杂不明.此外,水系电解液中存在的析氢竞争反应也为高效NO_(3)RR催化剂的开发设计带来了巨大的挑战.为突破高效催化剂的发展瓶颈,本文通过理论模拟,在低成本的催化剂上设计了高效的NO_(3)RR催化活性位点,并利用简单的制备策略合成了目标催化剂.同时,结合原位表征技术,阐明了NO_(3)RR的反应路径及催化机理.本文通过密度泛函理论(DFT)计算发现,Cu/TiO_(2)催化剂上的Cu-O-Ti-O_(v)结构具有较好的NO_(3)-还原活性,该结构不仅能够促进反应中间体NOx-的吸附和活化,还能有效抑制竞争析氢反应,从而降低NO_(3)RR的反应能垒.在该结构上,NO_(3)RR的反应路径为:NO_(3)^(*)→NO_(2)^(*)→HONO^(*)→NO^(*)→*NOH→*N→^(*)NH→*NH2→*NH_(3)→NH_(3).基于理论计算结果,分别采用浸渍法和尿素水解法制备了系列富含Cu-O-Ti-O_(v)结构的Cu/TiO_(2)催化剂.氮气等温吸附-脱附曲线、拉曼光谱(Raman)、电子顺磁共振波谱、X射线光电子能谱(XPS)和傅立叶红外光谱等结果发现,相比于采用浸渍法制备的系列Cu/TiO_(2)催化剂,采用尿素水解法制备的Cu/TiO_(2)(CT-U)催化剂具有更大的比表面积以及更多的Cu-O-Ti-O_(v)位点,说明尿素水解法可提高Cu颗粒在TiO_(2)载体表面的分散度,增强Cu颗粒与TiO_(2)载体之间的相互作用,提高Cu/TiO_(2)催化剂表面的Cu-O-Ti-O_(v)位点含量.将以上制备出的催化剂应用于催化NO_(3)RR中,结果表明,在-1.0 V vs.RHE还原电位下,CT-U催化剂上氨产率可达3046.5μg h^(-1) mgcat^(-1),高于大多数文献报道结果.循环稳定性测试结果表明,在Cu/TiO_(2)催化剂上构建Cu-O-Ti-O_(v)位点还能显著抑制电催化反应过程中Cu物种从Cu/TiO_(2)催化剂上溶出,从而显著增强催化剂的稳定性.此外,设计制备了不含氧空位的Cu/TiO_(2),TiO_(2)-x,Cu,Cu_(2)O以及CuO催化剂,并将其用于催化NO_(3)RR.结果发现,上述催化剂上的氨产率皆明显低于CT-U催化剂,说明Cu,Ti以及O_(v)构成的Cu-O-Ti-O_(v)结构具有较好的催化协同作用,从而显著提升了NO_(3)RR反应活性.最后,通过原位Raman及原位XPS表征检测反应中间体,验证了由DFT模拟出的NO_(3)RR反应路径.综上,通过在Cu/TiO_(2)催化剂上理论指导构建Cu-O-Ti-O_(v)活性位点,实现了NO_(3)RR性能的有效提升.Cu-O-Ti-O_(v)结构中的多位点协同作用不仅促进了NO_(x)-的吸附和活化,而且抑制了电催化过程中Cu物种从催化剂上的溶出,从而提高了催化剂的稳定性.本研究为设计高效稳定的NO_(3)RR催化剂提供了新思路.
