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2017Ä꣬Maria¿ÎÌâ×é²ÉÓõÈÌå»ý½þ×Õ·¨ÖƱ¸Á˵¥Ô­×Ó·ÖÉ¢µÄRh/ZSM-5ºÍRh/TiO2´ß»¯¼Á£¬ÔÚ150 ¡æµÄË®ÏàÌåϵºÍº¬Ò»Ñõ»¯Ì¼ºÍÑõÆøÆø·ÕÖн«¼×ÍéÖ±½Óת»¯Îª¼×´¼ºÍÒÒËᣨ×ÜÑ¡ÔñÐÔ60%-100%£©¡¢¼×´¼ÊÕÂʸߴï1.22 mmol/g-cat¡£ÀûÓÃ×ÏÍâ¿É¼û¹âÆס¢Í¬²½·øÉäÎüÊÕ¾«Ï¸½á¹¹Æס¢Í¸ÉäɨÃèµç¾µºÍÒ»Ñõ»¯Ì¼Âþ·´Éä¹âÆ×£¬Ö¤Ã÷ÁËRhÖ÷ÒªÒÔRh+µÄÐÎʽ±»Îȶ¨µØ궨ÔÚ·Ö×Óɸ¿×µÀÄÚ£¬¶øÒ»²¿·ÖÈܽâµÄRhÎïÖÖÎÞ´ß»¯»îÐÔ¡£Èçͼ4Ëùʾ£¬·Ö×Óɸ¿×µÀÄÚµÄRh+ÓëCO×÷ÓÃÉú³ÉRhI(CO)2»îÐÔÎïÖÖ£¬ÔÚË®ÏàºÍÑõÆø»·¾³ÖУ¬»î»¯¼×ÍéÉú³ÉRh-CH3ÎïÖÖ£»ËæºóO²åÈëÉú³ÉRh¨COCH3ÎïÖÖ£¬Ë®½âÊͷųöCH3OH£»Í¬Ê±COÖ±½Ó²åÈëÉú³ÉRh-COCH3£¬ÔÚÖÊ×ÓËáÐÔλÉÏË®½â£¬ÊͷųöCH3COOH¡£

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ͼ3. Proposed possible reaction mechanism of oxiadation methane on Rh/ZSM-5.

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Figure 4. TEM and CO-DRIFTS spectra of various Rh-ZSM-5.


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Figure 5. Catalyst characterization and methane oxidation reactions on Au-Pd colloids.

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Figure 6. Proposed reaction scheme for methane oxidation with H2O2 and O2.



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ͬÄ꣬Van Bokhoven¿ÎÌâ×éÒÔË®ÕôÆû×÷ΪÑõ»¯¼Á£¬²ÉÓ÷ֲ½²Ù×÷µÄ¹¤ÒÕ(¼×Íé·´Ó¦²½+Ë®Æû»î»¯²½)£¬ÔÚCu-MORÉÏʵÏÖÁË97%µÄ¼×´¼Ñ¡ÔñÐÔ[3]¡£Èçͼ7Ëùʾ£¬ÔÚµÚÒ»²½¼×Íéת»¯·´Ó¦ÖУ¬CH4·Ö×ÓÓë·Ö×ÓɸÖеľ§¸ñÑõO2-½áºÏÉú³É¼×Ñõ»ùCH3O£¬ÔÚ·Ö×ÓɸËáÐÔλÉÏÍѸ½²úÉúCH3OH£»Óë´Ëͬʱ£¬ÓÉÓÚ¾§¸ñÑõµÄÏûºÄ£¬Cu-MOR´ß»¯¼ÁÖеÄCu2+ת±äΪCu+¡£ËæºóÔÚµÚ¶þ²½Ë®Æû»î»¯ÖУ¬¾ßÓÐÑõ¿ÕλµÄCu+ÎïÖÖ´ÓH2O·Ö×ÓÖжá×ßO£¬ÊͷųöH2£»Í¬Ê±£¬ÓÉÓÚ¾§¸ñÑõµÄ²¹³ä£¬Cu-MOR´ß»¯¼ÁÖеÄCu+ÖØлָ´³ÉCu2+ÎïÖÖ£¬Íê³ÉÒ»¸ö´ß»¯Ñ­»·¡£

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Figure 7. Schematic representation of methane oxidation by water.

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Figure 8. (A) Methanol yield and selectivity at either 673 K (blue bars) or 473 K (green bars). (B) and (C) Mass spectra.

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Figure 9. (G) Time-resolved in situ FTIR spectra in methane conversion at 473 K. (I) Methoxy species vs Brønsted acid sites formed in methane conversion at 473 K.

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Au-Pd´ß»¯¼ÁÔòÓÉÓÚAu-PdºÏ½ðÖ®¼ä¶ÀÌصľàÀ룬ǡºÃO2µÄÁ½¸öO·Ö±ðÎü¸½ÔÚAu¡¢PdÉÏ£¬´ý½âÀëÓÖ²»ÄÜÍêÈ«½âÀëµÄ״̬£¬ÐγÉÒ»¸öËıßÐνṹ£¬²»ÖÁÓÚÍêÈ«½âÀë³ÉÁ½¸ö»îÐÔÑõ£¬´Ó¶ø±íÏÖ³öÈõµÄÑõ»¯ÐÔ£¬ÊÇCH4²¿·ÖÑõ»¯Éú³ÉCH3OH£¬¶ø²»ÊÇÍêÈ«Ñõ»¯Éú³ÉCOºÍCO2.

Keyword£ºmethane, methanol, selective oxidation, zeolite, single atom catalysis (SAC)



Reference£º
1.Shan, Junjun, Mengwei Li, Lawrence F. Allard, Sungsik Lee, and Maria Flytzani-Stephanopoulos. Mild Oxidation of Methane to Methanol or Acetic Acid on Supported Isolated Rhodium Catalysts. Nature 551, no. 7682 : 605¨C8.
2. Agarwal, Nishtha, Simon J. Freakley, Rebecca U. McVicker, Sultan M. Althahban, Nikolaos Dimitratos, Qian He, David J. Morgan, et al. Aqueous Au-Pd Colloids Catalyze Selective CH4 Oxidation to CH3OH with O2 under Mild Conditions. Science 358, no. 6360 (2017): 223¨C27.
3. Sushkevich, Vitaly L, Dennis Palagin, Marco Ranocchiari, and Jeroen A van Bokhoven. Selective Anaerobic Oxidation of Methane Enables Direct Synthesis of Methanol. Science 356, no. 6337 (May 5, 2017): 523 LP ¨C 527.

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