The research on electrocatalysts with relatively lower price than Pt and excellent electrocatalytic performance for the cathode oxygen reduction reaction(ORR) and anode methanol oxidation reaction(MOR) is vital for th...The research on electrocatalysts with relatively lower price than Pt and excellent electrocatalytic performance for the cathode oxygen reduction reaction(ORR) and anode methanol oxidation reaction(MOR) is vital for the development of direct methanol fuel cells(DMFCs). In this work, we develop a cyanogel-reduction method to synthesize reduced graphene oxide(rGO) supported highly dispersed PdNi alloy nanocrystals(PdNi/rGO) with high alloying degree and tunable Pd/Ni ratio. The large specific surface area and the d-band center downshift of Pd result in excellent activity of Pd4 Ni1/rGO nanohybrids for the ORR. The modification of Pd electronic structure can facilitate the adsorption of CH3 OH on Pd surface and the highly oxophilic property of Ni can eliminate/mitigate the COadsintermediates poisoning, which make PdNi/r GO nanohybrids possess superior MOR activity. In addition, rGO improve the stability of PdNi alloy nanocrystals for the ORR and MOR. Due to high activity and stability for the ORR and MOR, PdNi/rGO nanohybrids are promising to be an available bifunctional electrocatalyst in DMFCs.展开更多
There have been ever-growing demands to develop advanced electrocatalysts for renewable energy conversion over the past decade.As a promising platform for advanced electrocatalysts,reduced graphene oxide(rGO)has attra...There have been ever-growing demands to develop advanced electrocatalysts for renewable energy conversion over the past decade.As a promising platform for advanced electrocatalysts,reduced graphene oxide(rGO)has attracted substantial research interests in a variety of electrochemical energy conversion reactions.Its versatile utility is mainly attributed to unique physical and chemical properties,such as high specific surface area,tunable electronic structure,and the feasibility of structural modification and functionalization.Here,a comprehensive discussion is provided upon recent advances in the material preparation,characterization,and the catalytic activity of rGO-based electrocatalysts for various electrochemical energy conversion reactions(water splitting,CO2 reduction reaction,N2 reduction reaction,and O2 reduction reaction).Major advantages of rGO and the related challenges for enhancing their catalytic performance are addressed.展开更多
Electrochemical reduction of water to hydrogen holds great promise for clean energy,while its widespread application relies on the development of efficient catalysts with large surface area,abundant exposed active sit...Electrochemical reduction of water to hydrogen holds great promise for clean energy,while its widespread application relies on the development of efficient catalysts with large surface area,abundant exposed active sites and superior electron conductivity.Herein,we report a facile strategy to configure an electrocatalyst composed of cobalt phosphide and rhodium uniformly anchored on reduced graphene oxide for hydrogen generation.The hybrids effectively integrate the exposed active sites,electron conductivity and synergistic effect of the catalyst.Electrochemical tests exhibit that the catalyst shows superior hydrogen evolution reaction catalytic activity and stability,with a small Tafel slope of 43 m V dec-1.Overpotentials as low as 29 and 72 mV are required to achieve current densities of 2 and 10 mA cm-2in 0.5M H2SO4,respectively.The hybrid constitution with highly active sites on conductive substrate is a new strategy to synthesize extremely efficient electrocatalysts.Especially,the efficient synergistic effect among cobalt phosphide,rhodium and reduced graphene oxide provides a novel approach for configuring electrocatalysts with high electron efficiency.展开更多
In this paper, we report a simple and facile self-assembly method to successfully fabricate cationic metal porphyrin-MtTMPyP(Mt= Cobalt(Ⅱ), Manganese(Ⅲ), or Iron(Ⅲ); TMPyP = 5, 10, 15, 20-tetrakis(N-methylpyridiniu...In this paper, we report a simple and facile self-assembly method to successfully fabricate cationic metal porphyrin-MtTMPyP(Mt= Cobalt(Ⅱ), Manganese(Ⅲ), or Iron(Ⅲ); TMPyP = 5, 10, 15, 20-tetrakis(N-methylpyridinium-4-yl) porphyrin) intercalated into the layer of graphene oxide(GO) by the cooperative effects of electrostatic and π-π stacking interaction between positively charged metal porphyrin and negatively charged GO sheets. Followed by reduction with hydrazine vapor, a series of novel 2 D MtTMPyP/rGO_n were fabricated. The as-prepared 2 D hybrids were fully characterized and tested as non-noble metal catalysts for oxygen reduction reaction(ORR) in an alkaline medium. The MtTMPyP/rGO_n hybrids, especially CoTMPyP/rGO_5, demonstrated an improved electrocatalytic activity for ORR and a number of exchanged electrons close to 4-electron reaction, increased stability and excellent tolerance to methanol, showing a potential alternative catalyst for ORR in fuel cells and air batteries.展开更多
Porphyrin-functionalized reduced graphene oxide (RGO-TPP) was prepared by 1,3-dipolar cycloaddition reaction and characterized by Fourier transform infrared spectroscopy, Raman, ultraviolet/visible absorption, fluores...Porphyrin-functionalized reduced graphene oxide (RGO-TPP) was prepared by 1,3-dipolar cycloaddition reaction and characterized by Fourier transform infrared spectroscopy, Raman, ultraviolet/visible absorption, fluorescence, and transmission electron microscopy. At the same level of linear transmittance, RGO-TPP exhibited more enhanced optical nonlinearities than RGO and the pristineporphyrin, implying a remarkable accumulation effect as a result of the covalent link between RGO and porphyrin. The role of energy/electron transfer in the optical nonlinearities of RGO-TPP was investigated by fluorescence and Raman spectroscopy. All the results displayed that RGO can be covalently functionalized with porphyrins by the proposed approach.展开更多
As alternatives to Pt-based electrocatalysts, the development of nonprecious metal catalysts with high performance in the cathodic oxygen reduction reaction （ORR） is highly desirable for widespread use in fuel cells...As alternatives to Pt-based electrocatalysts, the development of nonprecious metal catalysts with high performance in the cathodic oxygen reduction reaction （ORR） is highly desirable for widespread use in fuel cells. Here we report a simple approach for preparing pentabasic （Fe, B, N, S, P）-doped reduced graphene oxide （rGO） via a two-step doping method of adding boric acid and ferric chloride to ternary （N, S, P）-doped rGO （NSPG）. Electro- chemical investigation of the composites for the ORR revealed that simultaneously doping appropriate amounts of Fe and B into the NSPG produced a synergistic effect that endowed the prepared catalyst with both a positively shifted ORR half-wave potential and high selectivity for the 4e^-reduction of O2. The optimized Fe2B-NSPG catalyst approached a 4e^- process for the ORR with a half-wave potential （E1/2=0.90 V vs. RHE） even 30 mV higher than that of the commercial Pt/C catalyst in alkaline solution. Furthermore, relative to the Pt/C catalyst, the Fe2B-NSPG demonstrated superior stability and excellent tolerance of the methanol cross-over effect. This simple method afforded pentabasic （Fe, B, N, S, P）-doped rGO as a promising nonpreeious metal catalyst used for alkaline fuel cells.展开更多
基金the National Natural Science Foundation of China (21473111)the Fundamental Research Funds for the Central Universities (GK201701007)
文摘The research on electrocatalysts with relatively lower price than Pt and excellent electrocatalytic performance for the cathode oxygen reduction reaction(ORR) and anode methanol oxidation reaction(MOR) is vital for the development of direct methanol fuel cells(DMFCs). In this work, we develop a cyanogel-reduction method to synthesize reduced graphene oxide(rGO) supported highly dispersed PdNi alloy nanocrystals(PdNi/rGO) with high alloying degree and tunable Pd/Ni ratio. The large specific surface area and the d-band center downshift of Pd result in excellent activity of Pd4 Ni1/rGO nanohybrids for the ORR. The modification of Pd electronic structure can facilitate the adsorption of CH3 OH on Pd surface and the highly oxophilic property of Ni can eliminate/mitigate the COadsintermediates poisoning, which make PdNi/r GO nanohybrids possess superior MOR activity. In addition, rGO improve the stability of PdNi alloy nanocrystals for the ORR and MOR. Due to high activity and stability for the ORR and MOR, PdNi/rGO nanohybrids are promising to be an available bifunctional electrocatalyst in DMFCs.
基金This study was supported by Korea Hydro&Nuclear Power Co.,Ltd.(No.:2018-Tech-21)the National Research Foundation of Korea(NRF)grant funded by the Korea government MSIT(2019M3E6A1064763).
文摘There have been ever-growing demands to develop advanced electrocatalysts for renewable energy conversion over the past decade.As a promising platform for advanced electrocatalysts,reduced graphene oxide(rGO)has attracted substantial research interests in a variety of electrochemical energy conversion reactions.Its versatile utility is mainly attributed to unique physical and chemical properties,such as high specific surface area,tunable electronic structure,and the feasibility of structural modification and functionalization.Here,a comprehensive discussion is provided upon recent advances in the material preparation,characterization,and the catalytic activity of rGO-based electrocatalysts for various electrochemical energy conversion reactions(water splitting,CO2 reduction reaction,N2 reduction reaction,and O2 reduction reaction).Major advantages of rGO and the related challenges for enhancing their catalytic performance are addressed.
基金National Key Research and Development Program of China (No. 2016YFB0701100)the National Natural Science Foundation of China (51802015)+1 种基金the Fundamental Research Funds for the Central Universities (FRF-TP-16-028A1)Program of Young Scholar sponsored by Beijing Organization Department (2017000020124G090) for financial support
文摘Electrochemical reduction of water to hydrogen holds great promise for clean energy,while its widespread application relies on the development of efficient catalysts with large surface area,abundant exposed active sites and superior electron conductivity.Herein,we report a facile strategy to configure an electrocatalyst composed of cobalt phosphide and rhodium uniformly anchored on reduced graphene oxide for hydrogen generation.The hybrids effectively integrate the exposed active sites,electron conductivity and synergistic effect of the catalyst.Electrochemical tests exhibit that the catalyst shows superior hydrogen evolution reaction catalytic activity and stability,with a small Tafel slope of 43 m V dec-1.Overpotentials as low as 29 and 72 mV are required to achieve current densities of 2 and 10 mA cm-2in 0.5M H2SO4,respectively.The hybrid constitution with highly active sites on conductive substrate is a new strategy to synthesize extremely efficient electrocatalysts.Especially,the efficient synergistic effect among cobalt phosphide,rhodium and reduced graphene oxide provides a novel approach for configuring electrocatalysts with high electron efficiency.
基金supported by Natural Science Fund of Jiangsu Province (BK20141247, BK20140447)Exceptional Talent Project in Jiangsu Province (2015-XCL-035)+3 种基金University Science Research Project of Jiangsu Province (13KJB430005, 11KJA430008)funded by the Priority Academic Program development of Jiangsu Higher Education InstitutionsJiangsu Province universities' "blue and green blue project"financial support from the ARC (CE140100012, FT130100380, and DP170102267)
文摘In this paper, we report a simple and facile self-assembly method to successfully fabricate cationic metal porphyrin-MtTMPyP(Mt= Cobalt(Ⅱ), Manganese(Ⅲ), or Iron(Ⅲ); TMPyP = 5, 10, 15, 20-tetrakis(N-methylpyridinium-4-yl) porphyrin) intercalated into the layer of graphene oxide(GO) by the cooperative effects of electrostatic and π-π stacking interaction between positively charged metal porphyrin and negatively charged GO sheets. Followed by reduction with hydrazine vapor, a series of novel 2 D MtTMPyP/rGO_n were fabricated. The as-prepared 2 D hybrids were fully characterized and tested as non-noble metal catalysts for oxygen reduction reaction(ORR) in an alkaline medium. The MtTMPyP/rGO_n hybrids, especially CoTMPyP/rGO_5, demonstrated an improved electrocatalytic activity for ORR and a number of exchanged electrons close to 4-electron reaction, increased stability and excellent tolerance to methanol, showing a potential alternative catalyst for ORR in fuel cells and air batteries.
文摘Porphyrin-functionalized reduced graphene oxide (RGO-TPP) was prepared by 1,3-dipolar cycloaddition reaction and characterized by Fourier transform infrared spectroscopy, Raman, ultraviolet/visible absorption, fluorescence, and transmission electron microscopy. At the same level of linear transmittance, RGO-TPP exhibited more enhanced optical nonlinearities than RGO and the pristineporphyrin, implying a remarkable accumulation effect as a result of the covalent link between RGO and porphyrin. The role of energy/electron transfer in the optical nonlinearities of RGO-TPP was investigated by fluorescence and Raman spectroscopy. All the results displayed that RGO can be covalently functionalized with porphyrins by the proposed approach.
文摘As alternatives to Pt-based electrocatalysts, the development of nonprecious metal catalysts with high performance in the cathodic oxygen reduction reaction （ORR） is highly desirable for widespread use in fuel cells. Here we report a simple approach for preparing pentabasic （Fe, B, N, S, P）-doped reduced graphene oxide （rGO） via a two-step doping method of adding boric acid and ferric chloride to ternary （N, S, P）-doped rGO （NSPG）. Electro- chemical investigation of the composites for the ORR revealed that simultaneously doping appropriate amounts of Fe and B into the NSPG produced a synergistic effect that endowed the prepared catalyst with both a positively shifted ORR half-wave potential and high selectivity for the 4e^-reduction of O2. The optimized Fe2B-NSPG catalyst approached a 4e^- process for the ORR with a half-wave potential （E1/2=0.90 V vs. RHE） even 30 mV higher than that of the commercial Pt/C catalyst in alkaline solution. Furthermore, relative to the Pt/C catalyst, the Fe2B-NSPG demonstrated superior stability and excellent tolerance of the methanol cross-over effect. This simple method afforded pentabasic （Fe, B, N, S, P）-doped rGO as a promising nonpreeious metal catalyst used for alkaline fuel cells.
