Direct CO_(2) hydrogenation offers an important strategy for promoting the global carbon balance,but high thermodynamic and kinetic stability of CO_(2) has restricted its applicability to only a handful of industrial ...Direct CO_(2) hydrogenation offers an important strategy for promoting the global carbon balance,but high thermodynamic and kinetic stability of CO_(2) has restricted its applicability to only a handful of industrial sectors.Here,we introduce a proof-of-concept application of the electron-rich Pt surface to promote hydrogen donation for electron-rich MoC particles acting as hydrogen acceptors,thereby constructing hydrogen-rich surface of MoC active centers.Moreover,the formed hydrogen-rich and electronrich surface could greatly decrease reaction activation energy to boost the efficient CO_(2) hydrogenation into formic acid over the MoC centers.The optimized MoC@NC/Pt-0.1(NC:nitrogen-doped carbon)catalyst exhibits a high turnover frequency(TOF)value of 1.2 h^(−1) at a lower temperature of 60℃and a TOF of 24.2 h^(−1) under standard reaction conditions widely used in the literature,exceeding 7 times of MoC@NC catalyst and surpassing the benchmark classical non-noble metal active center-based heterogeneous catalyst.展开更多
Dissociation of active H species over the catalytic sites with the carbon-supported Pt metals as the mainstream catalysts is crucial to facilitate hydrogen donation and accelerate the hydrogen addition process in cata...Dissociation of active H species over the catalytic sites with the carbon-supported Pt metals as the mainstream catalysts is crucial to facilitate hydrogen donation and accelerate the hydrogen addition process in catalytic hydrogenation systems to produce polymers,pharmaceuticals,agrochemicals,fragrances,and biofuels at million-ton scale.Much attention has been paid to the design of the more active catalytic site to effectively adsorb and activate reactants and H_(2) molecules.At the same time,there is still a huge room to develop powerful strategies to accelerate the donation of acted H species to the reactants from the Pt surface further to boost the final catalytic efficiencies of Pt catalysts and depress the total Pt consumption.Herein,we present a new strategy for promoting the Pt-H bond dissociation by increasing surface hydrogen coverage on designed electron-deficient Pt nanoparticles.The electron deficiency of Pt nanoparticles has been successfully tuned by constructing a rectifying contact with an even“noble”boron-rich carbon support(Pt/BC).Theoretical and experimental results confirm the dominant role of the pronounced electron deficiencies of Pt nanoparticles in enhancing the H coverage for 2.3 times higher than that of neutral Pt nanoparticles,significantly boosting the Pt-H bond dissociation and thus the whole hydrogenation process as reflected by the extremely high turnover frequency(TOF)value of 388 h^(-1)at 30℃ and 10 bar H_(2) for phenol hydrogenation on the Pt/BC,outperforming the bench-marked catalysts by a factor of 9.展开更多
Stable and portable ammonia(NH3)is a promising,low-cost,and environment-friendly medium for energy storage.How to achieve the rapid production of NH3 from reducing NO_(x)^(−)in aqueous systems and industrial wastewate...Stable and portable ammonia(NH3)is a promising,low-cost,and environment-friendly medium for energy storage.How to achieve the rapid production of NH3 from reducing NO_(x)^(−)in aqueous systems and industrial wastewater via electrochemical methods remains the main challenge for practical application on a large scale.The corresponding electrocatalysts as the key materials in electrochemical devices suffer from low activity,especially in neutral systems.In this work,we successfully elevated the activity of the bench-mark Ru electrocatalysts to more than 30 times via construction of rectifying contact of Ru metals and noble carbons.We theoretically predicted and then rationally designed a new type of P-O rich carbon with large work functions as“noble”supports to attract a pronounced number of electrons from Ru metals at the rectifying interface.The resulting electron deficiency of Ru metals largely promotes the pre-adsorption and activation of NO_(x)^(−)anions,providing high Faradaic efficiencies(>96%)and record-high turnover frequency values for universal NO_(2)^(−)and NO_(3)^(−)reduction in neutral solution.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22071146 and 21931005)the Shanghai Science and Technology Committee(No.23XD1421800)+1 种基金the Shanghai Shuguang Program(No.21SG12)the Shanghai Municipal Science and Technology Major Project.
文摘Direct CO_(2) hydrogenation offers an important strategy for promoting the global carbon balance,but high thermodynamic and kinetic stability of CO_(2) has restricted its applicability to only a handful of industrial sectors.Here,we introduce a proof-of-concept application of the electron-rich Pt surface to promote hydrogen donation for electron-rich MoC particles acting as hydrogen acceptors,thereby constructing hydrogen-rich surface of MoC active centers.Moreover,the formed hydrogen-rich and electronrich surface could greatly decrease reaction activation energy to boost the efficient CO_(2) hydrogenation into formic acid over the MoC centers.The optimized MoC@NC/Pt-0.1(NC:nitrogen-doped carbon)catalyst exhibits a high turnover frequency(TOF)value of 1.2 h^(−1) at a lower temperature of 60℃and a TOF of 24.2 h^(−1) under standard reaction conditions widely used in the literature,exceeding 7 times of MoC@NC catalyst and surpassing the benchmark classical non-noble metal active center-based heterogeneous catalyst.
基金This work was supported by the Shanghai Science and Technology Committee(No.20520711600)the National Natural Science Foundation of China(Nos.22071146 and 21931005)the SJTU-MPI partner group,and the Open Research Fund of the State Key Laboratory of Inorganic Synthesis and Preparative Chemistry(Jilin University,China,No.2021-1).
文摘Dissociation of active H species over the catalytic sites with the carbon-supported Pt metals as the mainstream catalysts is crucial to facilitate hydrogen donation and accelerate the hydrogen addition process in catalytic hydrogenation systems to produce polymers,pharmaceuticals,agrochemicals,fragrances,and biofuels at million-ton scale.Much attention has been paid to the design of the more active catalytic site to effectively adsorb and activate reactants and H_(2) molecules.At the same time,there is still a huge room to develop powerful strategies to accelerate the donation of acted H species to the reactants from the Pt surface further to boost the final catalytic efficiencies of Pt catalysts and depress the total Pt consumption.Herein,we present a new strategy for promoting the Pt-H bond dissociation by increasing surface hydrogen coverage on designed electron-deficient Pt nanoparticles.The electron deficiency of Pt nanoparticles has been successfully tuned by constructing a rectifying contact with an even“noble”boron-rich carbon support(Pt/BC).Theoretical and experimental results confirm the dominant role of the pronounced electron deficiencies of Pt nanoparticles in enhancing the H coverage for 2.3 times higher than that of neutral Pt nanoparticles,significantly boosting the Pt-H bond dissociation and thus the whole hydrogenation process as reflected by the extremely high turnover frequency(TOF)value of 388 h^(-1)at 30℃ and 10 bar H_(2) for phenol hydrogenation on the Pt/BC,outperforming the bench-marked catalysts by a factor of 9.
基金This work was supported by the National Natural Science Foundation of China(grant nos.21931005,21720102002,and 22071146)Shanghai Science and Technology Committee(grant nos.19JC1412600 and 20520711600),and the SJTU-MPI partner group.
文摘Stable and portable ammonia(NH3)is a promising,low-cost,and environment-friendly medium for energy storage.How to achieve the rapid production of NH3 from reducing NO_(x)^(−)in aqueous systems and industrial wastewater via electrochemical methods remains the main challenge for practical application on a large scale.The corresponding electrocatalysts as the key materials in electrochemical devices suffer from low activity,especially in neutral systems.In this work,we successfully elevated the activity of the bench-mark Ru electrocatalysts to more than 30 times via construction of rectifying contact of Ru metals and noble carbons.We theoretically predicted and then rationally designed a new type of P-O rich carbon with large work functions as“noble”supports to attract a pronounced number of electrons from Ru metals at the rectifying interface.The resulting electron deficiency of Ru metals largely promotes the pre-adsorption and activation of NO_(x)^(−)anions,providing high Faradaic efficiencies(>96%)and record-high turnover frequency values for universal NO_(2)^(−)and NO_(3)^(−)reduction in neutral solution.
