A facile template-free in situ self-activation approach for the multiple active components synergistically driven porous carbon was presented via a feasible annealing process.The biomass-derived carbon without additio...A facile template-free in situ self-activation approach for the multiple active components synergistically driven porous carbon was presented via a feasible annealing process.The biomass-derived carbon without additional activation reagents was fabricated using K-rich pomelo peel(PP)as the carbon source,which possesses a high electric conductivity where abundant functional hetero-metal atoms are doped into the carbon framework that playing the role of catalytic graphitization.The K^+that exists within the biomass can induce self-activation during pyrolysis apart from the activating gases during the pyrolysis process.The resulting electrocatalyst of PP-850(PP was pyrolyzed at 850°C in an N_2atmosphere)with abundant heteroatoms possesses a higher power conversion efficiency(PCE)of 7.81%as the counter electrode(CE)of dye-sensitized solar cells(DSCs)compared with the CEs calcinated at other temperatures and a similar PCE with Pt counterpart(8.24%)based on the liquid I_3^-/I^-electrolyte.The better electrocatalytic performance is attributed to the synergistic effect between self-activation and the co-doping of nitrogen,sulfur and phosphorus all together in a carbon matrix.Due to the feasibility of large-scale production,rich heteroatom doping,the PP-derived carbon,which simplifies the procedure and decreases the cost,has a potential application for an alternative electrocatalyst for high-performance photovoltaic devices.展开更多
Currently,pyrolysis as the most widely used method still has some key issues not well resolved for synthesis of carbon-supported single-atom catalysts(C-SACs),e.g.,the sintering of metal atoms at high temperature as w...Currently,pyrolysis as the most widely used method still has some key issues not well resolved for synthesis of carbon-supported single-atom catalysts(C-SACs),e.g.,the sintering of metal atoms at high temperature as well as the high cost and complicated preparations of precursors.In this report,molten salts are demonstrated to be marvellous medium for preparation of C-SACs by pyrolysis of small molecular precursors(ionic liquid).The ultrastrong polarity on one hand establishes robust interaction with precursor and enables better carbonization,resulting in largely enhanced yield.On the other hand,the aggregation of metal atoms is effectively refrained while no nanoparticle or cluster is formed.By this strategy,a C-SAC with atomically dispersed Fe-N_(4) sites and a high specific area over 2000 m^(2) g^(-1) is obtained,which illustrates high ORR activity in both acid and alkaline media.Moreover,this SAC exhibits superior methanol tolerance and stability after acid soaking at 85℃ for 48 h.It is believed that the molten-salts-assisted pyrolysis can be developed into a routine strategy as it not only can largely simply the synthesis of C-SACs,but also can be extended to prepare other types of SACs.展开更多
Impeding high temperature sintering is challengeable for synthesis of carbon-supported single-atom catalysts (C-SACs), which requires high-cost precursor and strictly-controlled procedures. Herein, by virtue of the ul...Impeding high temperature sintering is challengeable for synthesis of carbon-supported single-atom catalysts (C-SACs), which requires high-cost precursor and strictly-controlled procedures. Herein, by virtue of the ultrastrong polarity of salt melts, sintering of metal atoms is effectively suppressed. Meanwhile, doping with inorganic sulfur anions not only produces sufficient anchoring sites to achieve high loading of atomically dispersed Co up to 13.85 wt.%, but also enables their electronic and geometric structures to be well tuned. When served as a cathode catalyst in dye-sensitized solar cells, the C-SAC with Co-N4-S2 moieties exhibits high activity towards the iodide reduction reaction (IRR), achieving a higher power conversion efficiency than that of conventional Pt counterpart. Density function theory (DFT) calculations revealed that the superior IRR activity was ascribed to the unique structure of Co-N4-S2 moieties with lower reaction barriers and moderate binding energy of iodine on the Co center, which was beneficial to I2 dissociation.展开更多
基金financial assistance from the National Natural Science Foundation of China (Grant nos. 51402036 and 51773025)the International Science & Technology Cooperation Program of China (Grant no. 2013DFA51000)
文摘A facile template-free in situ self-activation approach for the multiple active components synergistically driven porous carbon was presented via a feasible annealing process.The biomass-derived carbon without additional activation reagents was fabricated using K-rich pomelo peel(PP)as the carbon source,which possesses a high electric conductivity where abundant functional hetero-metal atoms are doped into the carbon framework that playing the role of catalytic graphitization.The K^+that exists within the biomass can induce self-activation during pyrolysis apart from the activating gases during the pyrolysis process.The resulting electrocatalyst of PP-850(PP was pyrolyzed at 850°C in an N_2atmosphere)with abundant heteroatoms possesses a higher power conversion efficiency(PCE)of 7.81%as the counter electrode(CE)of dye-sensitized solar cells(DSCs)compared with the CEs calcinated at other temperatures and a similar PCE with Pt counterpart(8.24%)based on the liquid I_3^-/I^-electrolyte.The better electrocatalytic performance is attributed to the synergistic effect between self-activation and the co-doping of nitrogen,sulfur and phosphorus all together in a carbon matrix.Due to the feasibility of large-scale production,rich heteroatom doping,the PP-derived carbon,which simplifies the procedure and decreases the cost,has a potential application for an alternative electrocatalyst for high-performance photovoltaic devices.
基金financially supported by the National Natural Science Foundation of China(Grant No.51773025)the Natural Science Foundation of Liaoning Province(Materials Joint Foundation,Grant No.20180510027)Dalian science and technology innovation fund(Grant No.019J12GX032)。
文摘Currently,pyrolysis as the most widely used method still has some key issues not well resolved for synthesis of carbon-supported single-atom catalysts(C-SACs),e.g.,the sintering of metal atoms at high temperature as well as the high cost and complicated preparations of precursors.In this report,molten salts are demonstrated to be marvellous medium for preparation of C-SACs by pyrolysis of small molecular precursors(ionic liquid).The ultrastrong polarity on one hand establishes robust interaction with precursor and enables better carbonization,resulting in largely enhanced yield.On the other hand,the aggregation of metal atoms is effectively refrained while no nanoparticle or cluster is formed.By this strategy,a C-SAC with atomically dispersed Fe-N_(4) sites and a high specific area over 2000 m^(2) g^(-1) is obtained,which illustrates high ORR activity in both acid and alkaline media.Moreover,this SAC exhibits superior methanol tolerance and stability after acid soaking at 85℃ for 48 h.It is believed that the molten-salts-assisted pyrolysis can be developed into a routine strategy as it not only can largely simply the synthesis of C-SACs,but also can be extended to prepare other types of SACs.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.51773025 and 21701168)the Natural Foundation of Liaoning Province(Materials Joint Foundation,No.20180510027)+1 种基金Dalian Science and Technology Innovation Fund(No.019J12GX032)We gratefully acknowledge the BL14W1 Beamline of Shanghai Synchrotron Radiation Facility(SSRF)in Shanghai,China and the 1W1B Beamline of Beijing Synchrotron Radiation Facility(BSRF)in Beijing,China for providing the beam time.
文摘Impeding high temperature sintering is challengeable for synthesis of carbon-supported single-atom catalysts (C-SACs), which requires high-cost precursor and strictly-controlled procedures. Herein, by virtue of the ultrastrong polarity of salt melts, sintering of metal atoms is effectively suppressed. Meanwhile, doping with inorganic sulfur anions not only produces sufficient anchoring sites to achieve high loading of atomically dispersed Co up to 13.85 wt.%, but also enables their electronic and geometric structures to be well tuned. When served as a cathode catalyst in dye-sensitized solar cells, the C-SAC with Co-N4-S2 moieties exhibits high activity towards the iodide reduction reaction (IRR), achieving a higher power conversion efficiency than that of conventional Pt counterpart. Density function theory (DFT) calculations revealed that the superior IRR activity was ascribed to the unique structure of Co-N4-S2 moieties with lower reaction barriers and moderate binding energy of iodine on the Co center, which was beneficial to I2 dissociation.
