The direct oxidation of methane(CH_(4))into high-valued C1 oxygenates production has garnered increased attention in effectively using vast CH_(4)and alleviating the global energy crisis.However,due to the high cleava...The direct oxidation of methane(CH_(4))into high-valued C1 oxygenates production has garnered increased attention in effectively using vast CH_(4)and alleviating the global energy crisis.However,due to the high cleavage energy of C—H bond and low polarity of CH_(4)molecule,it is difficult to activate the first C—H bond.Furthermore,C1 oxygenates are readily inclined to be oxidized to CO_(2),because their weaker C—H bond comparing with CH_(4)molecule,resulting in poor selectivity.Herein,we designed ultrathin PdxAuy alloy NWs supported on ZSM-5(Z-5)to investigate the direct oxidation of CH_(4)to high value-added oxygenate under mild conditions.By precisely adjusting the molar ratio of Pd/Au and alloying degree,Pd9Au1NWs/Z-5 showed an excellent yield of 11.57 mmol·g^(–1)·h^(–1)and the outstanding selectivity of 95.1%for C1 oxygenates(CH_(3)OH,CH_(3)OOH and HCOOH).The in-situ spectroscopic and mechanism analysis proved that the enhanced catalytic performance of Pd_(9)Au_(1)NWs/Z-5 was ascribed to the stable one-dimensional nanostructure and the strong synergy effect with high alloying PdAu,which could increase the adsorption capacity of CH_(4)molecules on Pd atoms to promote the CH_(4)conversion.This work offers valuable insights into the design concept of high-efficient catalysts and the structure-activity relationship for the direct oxidation of CH_(4).展开更多
基金supported by the Hainan Province Science and Technology Special Fund(ZDYF2024SHFZ074,ZDYF2024SHFZ072)the National Natural Science Foundation of China(22109035,22202053,52164028,52274297,22309037)+4 种基金the Start-up Research Foundation of Hainan University(KYQD(ZR)-20008,20083,20084,21125,23035)the Opening Project of Key Laboratory of Electrochemical Energy Storage and Energy Conversion of Hainan Province(KFKT2021007)the collaborative Innovation Center of Marine Science and Technology,Hainan University(XTCX2022HYC04,XTCX2022HYC05)the Scientific Research Program Funded by Shaanxi Provincial Education Department(Program No.23JK0439)the specific research fund of The Innovation Platform for Academicians of Hainan Province(YSPTZX202315).
文摘The direct oxidation of methane(CH_(4))into high-valued C1 oxygenates production has garnered increased attention in effectively using vast CH_(4)and alleviating the global energy crisis.However,due to the high cleavage energy of C—H bond and low polarity of CH_(4)molecule,it is difficult to activate the first C—H bond.Furthermore,C1 oxygenates are readily inclined to be oxidized to CO_(2),because their weaker C—H bond comparing with CH_(4)molecule,resulting in poor selectivity.Herein,we designed ultrathin PdxAuy alloy NWs supported on ZSM-5(Z-5)to investigate the direct oxidation of CH_(4)to high value-added oxygenate under mild conditions.By precisely adjusting the molar ratio of Pd/Au and alloying degree,Pd9Au1NWs/Z-5 showed an excellent yield of 11.57 mmol·g^(–1)·h^(–1)and the outstanding selectivity of 95.1%for C1 oxygenates(CH_(3)OH,CH_(3)OOH and HCOOH).The in-situ spectroscopic and mechanism analysis proved that the enhanced catalytic performance of Pd_(9)Au_(1)NWs/Z-5 was ascribed to the stable one-dimensional nanostructure and the strong synergy effect with high alloying PdAu,which could increase the adsorption capacity of CH_(4)molecules on Pd atoms to promote the CH_(4)conversion.This work offers valuable insights into the design concept of high-efficient catalysts and the structure-activity relationship for the direct oxidation of CH_(4).
