Two-dimensional(2D)materials received large amount of studies because of the enormous potential in basic science and industrial applications.Monolayer Pd2Se3 is a fascinating 2D material that was predicted to possess ...Two-dimensional(2D)materials received large amount of studies because of the enormous potential in basic science and industrial applications.Monolayer Pd2Se3 is a fascinating 2D material that was predicted to possess excellent thermoelectric,electronic,transport,and optical properties.However,the fabrication of large-scale and high-quality monolayer Pd2Se3 is still challenging.Here,we report the synthesis of large-scale and high-quality monolayer Pd2Se3 on graphene-SiC(0001)by a two-step epitaxial growth.The atomic structure of Pd2Se3 was investigated by scanning tunneling microscope(STM)and confirmed by non-contact atomic force microscope(nc-AFM).Two subgroups of Se atoms have been identified by nc-AFM image in agreement with the theoretically predicted atomic structure.Scanning tunneling spectroscopy(STS)reveals a bandgap of 1.2 eV,suggesting that monolayer Pd2Se3 can be a candidate for photoelectronic applications.The atomic structure and defect levels of a single Se vacancy were also investigated.The spatial distribution of STS near the Se vacancy reveals a highly anisotropic electronic behavior.The two-step epitaxial synthesis and characterization of Pd2Se3 provide a promising platform for future investigations and applications.展开更多
以硝酸铝和尿素为原料,通过水热法成功合成富含五配位Al^(3+)的γ-Al_(2)O_(3)载体,采用XRD、SEM、STEM-HAADF、27Al MAS NMR、N_(2)吸附-脱附等手段表征了载体的物理化学性质,并对采用该载体制备的Pd/Al_(2)O_(3)催化剂进行了蒽醌加氢...以硝酸铝和尿素为原料,通过水热法成功合成富含五配位Al^(3+)的γ-Al_(2)O_(3)载体,采用XRD、SEM、STEM-HAADF、27Al MAS NMR、N_(2)吸附-脱附等手段表征了载体的物理化学性质,并对采用该载体制备的Pd/Al_(2)O_(3)催化剂进行了蒽醌加氢制H_(2)O_(2)的初步性能评价。表征结果显示,合成的载体中的五配位Al^(3+)相对含量可达40.88%(w),微观粒子呈棒状,棒的长度1~4μm,直径0.1~0.3μm,BET比表面积可达494 m^(2)/g;所制备的Pd/Al_(2)O_(3)催化剂中Pd纳米粒子分散良好,平均粒径为3.51 nm,且分布较窄。评价结果表明,该催化剂相对于参比剂具有较高的加氢活性。展开更多
Formaldehyde(HCHO)is a significant indoor pollutant found in various sources and poses potential health risks to humans.Noble metal catalysts show efficient and stable catalytic activity for ambient-temperature HCHO o...Formaldehyde(HCHO)is a significant indoor pollutant found in various sources and poses potential health risks to humans.Noble metal catalysts show efficient and stable catalytic activity for ambient-temperature HCHO oxidation,yet suffer from low metal utilization.Efforts focus on designing catalysts with enhanced intrinsic activity and reduced noble metal loading.In this study,we developed a simple pretreatment method using ammonia solution on SiO_(2)carrier to enhance the activity of the Pd/SiO_(2)catalyst for HCHO oxidation.After the carrier was pretreated with an ammonia solution,a significant promoting effect was observed on the Pd/SiO_(2)(NH_(3)·H_(2)O)-R catalyst.It achieved almost complete oxidation of 150 ppmV of HCHO at 25℃,much better than the Pd/SiO_(2)-R(5%HCHO conversion rate).Multiple characterization results indicated that the ammonia solution pretreatment of the SiO_(2)carrier increased the surface defects,facilitating the anchoring of Pd nanoparticles and increasing their dispersion.The increase dispersion of Pd resulted in the generation of additional oxygen vacancies on the catalyst surfaces.The increased in oxygen vacancies on the catalyst was beneficial for enhancing the catalyst's ability to activate H_(2)O to form surface hydroxyl groups,thereby accelerating the catalytic oxidation process of HCHO.The reaction mechanism of HCHO on the Pd/SiO_(2)(NH_(3)·H_(2)O)-R catalyst mainly follows an efficient pathway:firstly,the HCHO being oxidized by surface active hydroxyl groups to formate;subsequently,the formate being oxidized by hydroxyl groups to H_(2)O and CO_(2).This study provides a promising strategy for designing high-performance noble metal catalysts for HCHO catalytic oxidation.展开更多
Highly dispersed noble metals are acknowledged for its pivotal role in influencing the efficiency of catalysts during the HCHO oxidation process.Interestingly,in this work,an innovative approach was employed to augmen...Highly dispersed noble metals are acknowledged for its pivotal role in influencing the efficiency of catalysts during the HCHO oxidation process.Interestingly,in this work,an innovative approach was employed to augmenting the stabilization of noble metals on irreducible carriers supported noble metal catalyst(Pd/SiO_(2))by adding alkali metal potassium(K).A formidable promotion effect was observed when the K doping to Pd/SiO_(2) catalysts.It achieves a conversion rate of 93%for 270 ppmV of HCHO to harmless CO_(2) and H_(2)O at a weight hourly space velocity(WHSV)of 300,000 mL/(g·hr)at 25℃.Multiple characterization results illustrated that a strong interaction between added K and Pd species was formed after K addition,which not only stabilized Pd species on the carrier surface but alsomarkedly enhanced its dispersal on the SiO_(2) carrier.The increasing Pd dispersion induced more oxygen vacancies on the surfaces of the Pd/SiO_(2) catalysts.The formation of these oxygen vacancies can be attributed to the phenomenon of hydrogen spillover,which also contributed to elevating the electron density on the Pd sites.Meanwhile,the oxygen vacancies favored the O_(2) activation to formmore reactive oxygen species participating in the HCHO oxidation reaction,thus improving the performance of Pd/SiO_(2) catalysts displayed for HCHO oxidation.This study provides a simple strategy to design high-performance irreducible carriers supported noble metal catalysts for HCHO catalytic oxidation.展开更多
Electrochemical nitrate(NO_(3)^(-))reduction reaction(eNO_(3)RR)to ammonia(NH3)provides a promising route for both water conservation and green ammonia synthesis.Although various catalysts were designed for the eNO_(3...Electrochemical nitrate(NO_(3)^(-))reduction reaction(eNO_(3)RR)to ammonia(NH3)provides a promising route for both water conservation and green ammonia synthesis.Although various catalysts were designed for the eNO_(3)RR and great achievements have been achieved,it is still a challenge to realize selective eNO_(3)RR to NH3at low concentration for the competing hydrogen evolution reaction(HER)and poor mass transfer of NO_(3)^(-).Herein,we designed a tandem catalyst of Pd nanoparticle loaded Cu_(2)O hierarchical nanofiber(Pd-Cu_(2)O)to improve eNO_(3)RR performance at low nitrate concentration.The Pd-Cu_(2)O shows a faraday efficiency(FE)of 95.80%and an ammonia selectivity of 97.34%at a comparatively low applied potential of-0.15 V versus RHE with low concentration.Besides,it exhibits excellent nitrate removal effects,the residual concentration of nitrate-N was only 7.22 ppm at-0.15 V.Electrochemical characterizations indicate that the abundant secondary heterojunction structures and the tandem effects of Pd-Cu_(2)O synergistic ally accelerate the transfer and conversion of NO_(3)^(-)and improve the dynamic of eNO_(3)RR at low concentration.Furthermore,the operando electrochemical impedance spectroscopy(EIS)and density functional theory(DFT)calculations suggested the tandem effects of Pd-Cu_(2)O improved the adsorption of NO_(3)^(-)and*H and thus promoted the dynamics of eNO_(3)RR at low concentration.The findings highlight the tandem effects of Pd-Cu_(2)O and provide an effective strategy for designing electrocatalysts that can be applied to low concentration and low applied potential conditions.展开更多
Owing to the ppb-level detection standard toward the toxic and harmful gas,the detection of trace gases has become an important subject in the field of indoor environment management.However,the traditional resistive g...Owing to the ppb-level detection standard toward the toxic and harmful gas,the detection of trace gases has become an important subject in the field of indoor environment management.However,the traditional resistive gas sensors hardly meet the requirement due to the weak signal generated by trace gas molecules that are difficult to capture.Herein,a visible-light-assisted Pd/TiO_(2)gas sensor is proposed to endow the effective detection of trace formaldehyde(HCHO)gas without heating temperature.Benefiting from the enhanced photocatalytic properties of TiO_(2)by Pd decoration,the visible-light-assisted Pd/TiO_(2)gas sensor can detect the HCHO gas as low as80×10^(–9)at room temperature.The successful preparation of nanoscale TiO_(2)sensing layer is facilitated by the ultrathin carbon nanotube interdigital electrode in the gas sensor,which avoids the discontinuity of the sensing layer caused by the excessive thickness of the traditional metal electrode.In addition,the whole preparation process of the Pd/TiO_(2)gas sensor with carbon nanotube electrodes is compatible with mainstream CMOS fabrication technology,which is expected to realize the batch fabrication and micro-integrated application of gas sensors.It is expected that our work can provide a new strategy for the batch preparation of high-performance trace HCHO gas sensors and their future applications in portable electronic devices such as smartphones.展开更多
基金Project supported by the National Key Research and Development Program of China(Grant Nos.2016YFA0202300,2018YFA0305800,and 2019YFA0308500)the National Natural Science Foundation of China(Grant Nos.51922011,51872284,and 61888102)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant Nos.XDB30000000 and XDB28000000)the Science Fund from University of the Chinese Academy of Sciences.
文摘Two-dimensional(2D)materials received large amount of studies because of the enormous potential in basic science and industrial applications.Monolayer Pd2Se3 is a fascinating 2D material that was predicted to possess excellent thermoelectric,electronic,transport,and optical properties.However,the fabrication of large-scale and high-quality monolayer Pd2Se3 is still challenging.Here,we report the synthesis of large-scale and high-quality monolayer Pd2Se3 on graphene-SiC(0001)by a two-step epitaxial growth.The atomic structure of Pd2Se3 was investigated by scanning tunneling microscope(STM)and confirmed by non-contact atomic force microscope(nc-AFM).Two subgroups of Se atoms have been identified by nc-AFM image in agreement with the theoretically predicted atomic structure.Scanning tunneling spectroscopy(STS)reveals a bandgap of 1.2 eV,suggesting that monolayer Pd2Se3 can be a candidate for photoelectronic applications.The atomic structure and defect levels of a single Se vacancy were also investigated.The spatial distribution of STS near the Se vacancy reveals a highly anisotropic electronic behavior.The two-step epitaxial synthesis and characterization of Pd2Se3 provide a promising platform for future investigations and applications.
文摘以硝酸铝和尿素为原料,通过水热法成功合成富含五配位Al^(3+)的γ-Al_(2)O_(3)载体,采用XRD、SEM、STEM-HAADF、27Al MAS NMR、N_(2)吸附-脱附等手段表征了载体的物理化学性质,并对采用该载体制备的Pd/Al_(2)O_(3)催化剂进行了蒽醌加氢制H_(2)O_(2)的初步性能评价。表征结果显示,合成的载体中的五配位Al^(3+)相对含量可达40.88%(w),微观粒子呈棒状,棒的长度1~4μm,直径0.1~0.3μm,BET比表面积可达494 m^(2)/g;所制备的Pd/Al_(2)O_(3)催化剂中Pd纳米粒子分散良好,平均粒径为3.51 nm,且分布较窄。评价结果表明,该催化剂相对于参比剂具有较高的加氢活性。
基金supported by the Sanming University(No.23YG05)the Science Foundation of Fujian Province(No.2023J011027).
文摘Formaldehyde(HCHO)is a significant indoor pollutant found in various sources and poses potential health risks to humans.Noble metal catalysts show efficient and stable catalytic activity for ambient-temperature HCHO oxidation,yet suffer from low metal utilization.Efforts focus on designing catalysts with enhanced intrinsic activity and reduced noble metal loading.In this study,we developed a simple pretreatment method using ammonia solution on SiO_(2)carrier to enhance the activity of the Pd/SiO_(2)catalyst for HCHO oxidation.After the carrier was pretreated with an ammonia solution,a significant promoting effect was observed on the Pd/SiO_(2)(NH_(3)·H_(2)O)-R catalyst.It achieved almost complete oxidation of 150 ppmV of HCHO at 25℃,much better than the Pd/SiO_(2)-R(5%HCHO conversion rate).Multiple characterization results indicated that the ammonia solution pretreatment of the SiO_(2)carrier increased the surface defects,facilitating the anchoring of Pd nanoparticles and increasing their dispersion.The increase dispersion of Pd resulted in the generation of additional oxygen vacancies on the catalyst surfaces.The increased in oxygen vacancies on the catalyst was beneficial for enhancing the catalyst's ability to activate H_(2)O to form surface hydroxyl groups,thereby accelerating the catalytic oxidation process of HCHO.The reaction mechanism of HCHO on the Pd/SiO_(2)(NH_(3)·H_(2)O)-R catalyst mainly follows an efficient pathway:firstly,the HCHO being oxidized by surface active hydroxyl groups to formate;subsequently,the formate being oxidized by hydroxyl groups to H_(2)O and CO_(2).This study provides a promising strategy for designing high-performance noble metal catalysts for HCHO catalytic oxidation.
基金supported by the Youth Innovation Promotion Association,CAS(No.2020310)Sanming University(No.23YG05).
文摘Highly dispersed noble metals are acknowledged for its pivotal role in influencing the efficiency of catalysts during the HCHO oxidation process.Interestingly,in this work,an innovative approach was employed to augmenting the stabilization of noble metals on irreducible carriers supported noble metal catalyst(Pd/SiO_(2))by adding alkali metal potassium(K).A formidable promotion effect was observed when the K doping to Pd/SiO_(2) catalysts.It achieves a conversion rate of 93%for 270 ppmV of HCHO to harmless CO_(2) and H_(2)O at a weight hourly space velocity(WHSV)of 300,000 mL/(g·hr)at 25℃.Multiple characterization results illustrated that a strong interaction between added K and Pd species was formed after K addition,which not only stabilized Pd species on the carrier surface but alsomarkedly enhanced its dispersal on the SiO_(2) carrier.The increasing Pd dispersion induced more oxygen vacancies on the surfaces of the Pd/SiO_(2) catalysts.The formation of these oxygen vacancies can be attributed to the phenomenon of hydrogen spillover,which also contributed to elevating the electron density on the Pd sites.Meanwhile,the oxygen vacancies favored the O_(2) activation to formmore reactive oxygen species participating in the HCHO oxidation reaction,thus improving the performance of Pd/SiO_(2) catalysts displayed for HCHO oxidation.This study provides a simple strategy to design high-performance irreducible carriers supported noble metal catalysts for HCHO catalytic oxidation.
基金financially supported by the National Key Research and Development Program of China(No.2021YFB4000604)National Natural Science Foundation of China(No.52271220)+2 种基金The Program of the Ministry of Education of China for Introducing Talents of Discipline to Universities(No.B12015)the Fundamental Research Funds for the Central UniversitiesHaihe Laboratory of Sustainable Chemical Transformations,Guangxi Collaborative Innovation Centre of Structure and Property for New Energy and Materials,Science Research and Technology Development Project of Guilin(No.20210102-4)
文摘Electrochemical nitrate(NO_(3)^(-))reduction reaction(eNO_(3)RR)to ammonia(NH3)provides a promising route for both water conservation and green ammonia synthesis.Although various catalysts were designed for the eNO_(3)RR and great achievements have been achieved,it is still a challenge to realize selective eNO_(3)RR to NH3at low concentration for the competing hydrogen evolution reaction(HER)and poor mass transfer of NO_(3)^(-).Herein,we designed a tandem catalyst of Pd nanoparticle loaded Cu_(2)O hierarchical nanofiber(Pd-Cu_(2)O)to improve eNO_(3)RR performance at low nitrate concentration.The Pd-Cu_(2)O shows a faraday efficiency(FE)of 95.80%and an ammonia selectivity of 97.34%at a comparatively low applied potential of-0.15 V versus RHE with low concentration.Besides,it exhibits excellent nitrate removal effects,the residual concentration of nitrate-N was only 7.22 ppm at-0.15 V.Electrochemical characterizations indicate that the abundant secondary heterojunction structures and the tandem effects of Pd-Cu_(2)O synergistic ally accelerate the transfer and conversion of NO_(3)^(-)and improve the dynamic of eNO_(3)RR at low concentration.Furthermore,the operando electrochemical impedance spectroscopy(EIS)and density functional theory(DFT)calculations suggested the tandem effects of Pd-Cu_(2)O improved the adsorption of NO_(3)^(-)and*H and thus promoted the dynamics of eNO_(3)RR at low concentration.The findings highlight the tandem effects of Pd-Cu_(2)O and provide an effective strategy for designing electrocatalysts that can be applied to low concentration and low applied potential conditions.
基金financially supported by the National Natural Science Foundation of China(Nos.62071410 and 62101477)Hunan Provincial Natural Science Foundation(No.2021JJ40542)the Postgraduate Scientific Research Innovation Project of Hunan Province(No.CX20210627)。
文摘Owing to the ppb-level detection standard toward the toxic and harmful gas,the detection of trace gases has become an important subject in the field of indoor environment management.However,the traditional resistive gas sensors hardly meet the requirement due to the weak signal generated by trace gas molecules that are difficult to capture.Herein,a visible-light-assisted Pd/TiO_(2)gas sensor is proposed to endow the effective detection of trace formaldehyde(HCHO)gas without heating temperature.Benefiting from the enhanced photocatalytic properties of TiO_(2)by Pd decoration,the visible-light-assisted Pd/TiO_(2)gas sensor can detect the HCHO gas as low as80×10^(–9)at room temperature.The successful preparation of nanoscale TiO_(2)sensing layer is facilitated by the ultrathin carbon nanotube interdigital electrode in the gas sensor,which avoids the discontinuity of the sensing layer caused by the excessive thickness of the traditional metal electrode.In addition,the whole preparation process of the Pd/TiO_(2)gas sensor with carbon nanotube electrodes is compatible with mainstream CMOS fabrication technology,which is expected to realize the batch fabrication and micro-integrated application of gas sensors.It is expected that our work can provide a new strategy for the batch preparation of high-performance trace HCHO gas sensors and their future applications in portable electronic devices such as smartphones.
