分别采用光沉积法和浸渍法制备了载钯石墨相氮化碳催化剂(Pd/g-C3N4-PD和Pd/g-C3N4-IMP),并对其进行了电感耦合等离子体发射光谱(ICP-AES)、X射线衍射(XRD)、透射电镜(TEM)和Zeta电位的表征.结果表明,不同载钯量Pd/g-C3N4-PD的等电点均...分别采用光沉积法和浸渍法制备了载钯石墨相氮化碳催化剂(Pd/g-C3N4-PD和Pd/g-C3N4-IMP),并对其进行了电感耦合等离子体发射光谱(ICP-AES)、X射线衍射(XRD)、透射电镜(TEM)和Zeta电位的表征.结果表明,不同载钯量Pd/g-C3N4-PD的等电点均在p H 2.3左右;Pd/g-C3N4-PD表面Pd粒子分散均匀,且Pd粒径小于Pd/g-C3N4-IMP.分别将Pd/g-C3N4-PD和Pd/g-C3N4-IMP用于2,4-二氯酚的催化加氢脱氯研究,Pd/g-C3N4-PD的催化脱氯效果明显优于Pd/g-C3N4-IMP.低p H值利于2,4-二氯酚的催化加氢脱氯过程,但不利于保持催化剂的稳定性.展开更多
Selective hydrogenation is an important industrial catalytic process in chemical upgrading, where Pd-based catalysts are widely used because of their high hydrogenation activities. However, poor selectivity and short ...Selective hydrogenation is an important industrial catalytic process in chemical upgrading, where Pd-based catalysts are widely used because of their high hydrogenation activities. However, poor selectivity and short catalyst lifetime because of heavy coke formation have been major concerns. In this work, atomically dispersed Pd atoms were successfully synthesized on graphitic carbon nitride （g-C3N4） using atomic layer deposition. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy （HAADF-STEM） confirmed the dominant presence of isolated Pd atoms without Pd nanoparticle （NP） formation. During selective hydrogenation of acetylene in excess ethylene, the g-C3N4-supported Pd NP catalysts had strikingly higher ethylene selectivities than the conventional Pd/Al2O3 and Pd/SiO2 catalysts. In-situ X-ray photoemission spectroscopy revealed that the considerable charge transfer from the Pd NPs to g-C3N4 likely plays an important role in the catalytic performance enhancement. More impressively, the single-atom Pd1/C3N4 catalyst exhibited both higher ethylene selectivity and higher coking resistance. Our work demonstrates that the single-atom Pd catalyst is a promising candidate for improving both selectivity and coking-resistance in hydrogenation reactions.展开更多
The preparation of highly active electrocatalysts with good durability and low cost for fuel cells is highly desir- able but still remains a significant challenge. Here we synthesized two dimensional （2D） C3N4 nanos...The preparation of highly active electrocatalysts with good durability and low cost for fuel cells is highly desir- able but still remains a significant challenge. Here we synthesized two dimensional （2D） C3N4 nanosheets supported palladium composites （C3N4/Pd） via a simple and convenient sonochemical approach. We have systematically stud- ied the electrocatalytic performance of as-prepared catalysts. We found that the prepared C3N4/Pd composites pos- sessed excellent catalytic activity and stability for oxygen reduction reaction （ORR） in alkaline media. Encourag- ingly, the C3N4/Pd catalysts exhibit the excellent electrocatalytic activity for methanol oxidation reaction （MOR） in alkaline media, even better than that of the commercial Pt/C catalyst, The excellent electrocatalytic performance of the 2D C3N4 nanosheets supported palladium composites catalysts results from their synergy effect between the ul- trathin substrate material with large surface area and excellent dispersion of palladium nanoparticles. This study demonstrates that sonochemical method opens up a new avenue for the preparation of electrocatalysts for fuel cells. We expect these materials are likely to find uses in a broad range of applications, for example, fuel cells, solar cells, batteries and other electrochemical analysis.展开更多
文摘分别采用光沉积法和浸渍法制备了载钯石墨相氮化碳催化剂(Pd/g-C3N4-PD和Pd/g-C3N4-IMP),并对其进行了电感耦合等离子体发射光谱(ICP-AES)、X射线衍射(XRD)、透射电镜(TEM)和Zeta电位的表征.结果表明,不同载钯量Pd/g-C3N4-PD的等电点均在p H 2.3左右;Pd/g-C3N4-PD表面Pd粒子分散均匀,且Pd粒径小于Pd/g-C3N4-IMP.分别将Pd/g-C3N4-PD和Pd/g-C3N4-IMP用于2,4-二氯酚的催化加氢脱氯研究,Pd/g-C3N4-PD的催化脱氯效果明显优于Pd/g-C3N4-IMP.低p H值利于2,4-二氯酚的催化加氢脱氯过程,但不利于保持催化剂的稳定性.
基金Acknowledgements This work was supported by the Thousand Talents Plan, the National Natural Science Foundation of China （Nos. 21473169, 21673215, and 51402283）, the Fundamental Research Funds for the Central Universities （Nos. WK2060030017 and WK2060190026）, and the startup funds from the University of Science and Technology of China. This work was also supported by Hefei Science Center （No. 2015HSC-UP010）.
文摘Selective hydrogenation is an important industrial catalytic process in chemical upgrading, where Pd-based catalysts are widely used because of their high hydrogenation activities. However, poor selectivity and short catalyst lifetime because of heavy coke formation have been major concerns. In this work, atomically dispersed Pd atoms were successfully synthesized on graphitic carbon nitride （g-C3N4） using atomic layer deposition. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy （HAADF-STEM） confirmed the dominant presence of isolated Pd atoms without Pd nanoparticle （NP） formation. During selective hydrogenation of acetylene in excess ethylene, the g-C3N4-supported Pd NP catalysts had strikingly higher ethylene selectivities than the conventional Pd/Al2O3 and Pd/SiO2 catalysts. In-situ X-ray photoemission spectroscopy revealed that the considerable charge transfer from the Pd NPs to g-C3N4 likely plays an important role in the catalytic performance enhancement. More impressively, the single-atom Pd1/C3N4 catalyst exhibited both higher ethylene selectivity and higher coking resistance. Our work demonstrates that the single-atom Pd catalyst is a promising candidate for improving both selectivity and coking-resistance in hydrogenation reactions.
基金We greatly appreciate the support of the National Natural Science Foundation of China （Nos. 21475057, 21335004,） and the Program B tbr Outstanding PhD Candidates of Nanjing University. This work was also supported by the Program for New Century Excellent Talents in University （No. NCET-12-0256）.
文摘The preparation of highly active electrocatalysts with good durability and low cost for fuel cells is highly desir- able but still remains a significant challenge. Here we synthesized two dimensional （2D） C3N4 nanosheets supported palladium composites （C3N4/Pd） via a simple and convenient sonochemical approach. We have systematically stud- ied the electrocatalytic performance of as-prepared catalysts. We found that the prepared C3N4/Pd composites pos- sessed excellent catalytic activity and stability for oxygen reduction reaction （ORR） in alkaline media. Encourag- ingly, the C3N4/Pd catalysts exhibit the excellent electrocatalytic activity for methanol oxidation reaction （MOR） in alkaline media, even better than that of the commercial Pt/C catalyst, The excellent electrocatalytic performance of the 2D C3N4 nanosheets supported palladium composites catalysts results from their synergy effect between the ul- trathin substrate material with large surface area and excellent dispersion of palladium nanoparticles. This study demonstrates that sonochemical method opens up a new avenue for the preparation of electrocatalysts for fuel cells. We expect these materials are likely to find uses in a broad range of applications, for example, fuel cells, solar cells, batteries and other electrochemical analysis.
