Palladium-exchanged chabazite(Pd-CHA) zeolites as passive NO_x adsorbers(PNAs) enable efficient purification of nitrogen oxides(NO_x) in cold-start diesel exhausts. Their commercial application, however,is limited by ...Palladium-exchanged chabazite(Pd-CHA) zeolites as passive NO_x adsorbers(PNAs) enable efficient purification of nitrogen oxides(NO_x) in cold-start diesel exhausts. Their commercial application, however,is limited by the lack of facile preparation method. Here, high-performance CHA-type Pd-SAPO-34 zeolite was synthesized by a modified solid-state ion exchange(SSIE) method using PdO as Pd precursor,and demonstrated superior PNA performance as compared to Pd-SAPO-34 prepared by conventional wetchemistry strategies. Structural characterization using Raman spectroscopy and X-ray diffraction revealed that the SSIE method avoided water-induced damage to the zeolite framework during Pd loading. Mechanistic investigations on the SSIE process by in situ infrared spectroscopy and X-ray photoelectron spectroscopy disclosed that, while PdO precursor was mainly converted to Pd^(2+) cations coordinated to the zeolite framework by consuming the-OH groups of the zeolite, a portion of PdO could also undergo thermal decomposition to form highly dispersed Pd~0 clusters in the pore channels. This simplified and scalable SSIE method paves a new way for the cost-effective synthesis of defect-free high-performance Pd-SAPO-34 zeolites as PNA catalysts.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
Single-atom catalysts(SACs) with well-defined and specific single-atom dispersion on supports offer great potential for achieving both high catalytic activity and selectivity. Covalent organic frameworks(COFs) with ta...Single-atom catalysts(SACs) with well-defined and specific single-atom dispersion on supports offer great potential for achieving both high catalytic activity and selectivity. Covalent organic frameworks(COFs) with tailormade crystalline structures and designable atomic composition is a class of promising supports for SACs. Herein, we have studied the binding sites and stability of Pd single atoms(SAs)dispersed on triazine COF(Pd1/trzn-COF) and the reaction mechanism of CO oxidation using the density functional theory(DFT). By evaluating different adsorption sites, including the nucleophilic sp2C atoms, heteroatoms and the conjugated π-electrons of aromatic ring and triazine, it is found that Pd SAs can stably combine with trzn-COF with a binding energy around-5.0 eV, and there are two co-existing dynamic Pd1/trzn-COFs due to the adjacent binding sites on trzn-COF. The reaction activities of CO oxidation on Pd1/trzn-COF can be regulated by the anion–π interaction between a +δ phenyl center and the related-δ moieties as well as the electron-withdrawing feature of imine in the specific complexes. The Pd1/trzn-COF catalyst is found to have a high catalytic activity for CO oxidation via a plausible tri-molecular Eley-Rideal(TER) reaction mechanism. This work provides insights into the d–π interaction between Pd SAs and trznCOF, and helps to better understand and design new SACs supported on COF nanomaterials.展开更多
基金supported by the National Natural Science Foundation of China (No.21976058)the Natural Science Foundation of Guangdong Province (No.2023A1515011682)+3 种基金the Fundamental Research Funds for the Central Universities (No.2022ZYGXZR018)the National Engineering Laboratory for Mobile Source Emission Control Technology (No.NELMS2020A10)the funding from the Pearl River Talent Recruitment Program of Guangdong Province (No.2019QN01L170)the Innovation & Entrepreneurship Talent Program of Shaoguan City。
文摘Palladium-exchanged chabazite(Pd-CHA) zeolites as passive NO_x adsorbers(PNAs) enable efficient purification of nitrogen oxides(NO_x) in cold-start diesel exhausts. Their commercial application, however,is limited by the lack of facile preparation method. Here, high-performance CHA-type Pd-SAPO-34 zeolite was synthesized by a modified solid-state ion exchange(SSIE) method using PdO as Pd precursor,and demonstrated superior PNA performance as compared to Pd-SAPO-34 prepared by conventional wetchemistry strategies. Structural characterization using Raman spectroscopy and X-ray diffraction revealed that the SSIE method avoided water-induced damage to the zeolite framework during Pd loading. Mechanistic investigations on the SSIE process by in situ infrared spectroscopy and X-ray photoelectron spectroscopy disclosed that, while PdO precursor was mainly converted to Pd^(2+) cations coordinated to the zeolite framework by consuming the-OH groups of the zeolite, a portion of PdO could also undergo thermal decomposition to form highly dispersed Pd~0 clusters in the pore channels. This simplified and scalable SSIE method paves a new way for the cost-effective synthesis of defect-free high-performance Pd-SAPO-34 zeolites as PNA catalysts.
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supported by the National Natural Science Foundation of China (22033005,21590792 and 21763006)Guangdong Provincial Key Laboratory of Catalysis (2020B121201002)。
文摘Single-atom catalysts(SACs) with well-defined and specific single-atom dispersion on supports offer great potential for achieving both high catalytic activity and selectivity. Covalent organic frameworks(COFs) with tailormade crystalline structures and designable atomic composition is a class of promising supports for SACs. Herein, we have studied the binding sites and stability of Pd single atoms(SAs)dispersed on triazine COF(Pd1/trzn-COF) and the reaction mechanism of CO oxidation using the density functional theory(DFT). By evaluating different adsorption sites, including the nucleophilic sp2C atoms, heteroatoms and the conjugated π-electrons of aromatic ring and triazine, it is found that Pd SAs can stably combine with trzn-COF with a binding energy around-5.0 eV, and there are two co-existing dynamic Pd1/trzn-COFs due to the adjacent binding sites on trzn-COF. The reaction activities of CO oxidation on Pd1/trzn-COF can be regulated by the anion–π interaction between a +δ phenyl center and the related-δ moieties as well as the electron-withdrawing feature of imine in the specific complexes. The Pd1/trzn-COF catalyst is found to have a high catalytic activity for CO oxidation via a plausible tri-molecular Eley-Rideal(TER) reaction mechanism. This work provides insights into the d–π interaction between Pd SAs and trznCOF, and helps to better understand and design new SACs supported on COF nanomaterials.
