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ÎĽÜÖíÖí: ½ð±Ò+100, ¡ï¡ï¡ï¡ï¡ï×î¼Ñ´ð°¸ 2016-08-21 22:42:14
Æø»¯·´Ó¦ Ê×ÏÈÊÇ CO2 ±» ̼±íÃæ ËùÎü¸½£¬Ëæ×ŠζȵÄÉý¸ß£¬Ö±ÏßÐͽṹµÄ CO2·Ö×Ó¼ü ±» À­³¤ Ö±ÖÁ ¶ÏÁÑ£¬·ÖÁѳö µÄ 1¸öOÔ­×Ó ºÍ ʣϵÄ=C=O ·Ö±ðÔÚ ¾ßÓв»±¥ºÍ¼üµÄ 2¸öCÔ­×ÓÉÏ ÐÎ³É Á½¸ö»ùÍÅ£¬¼´ ͪ»ù(>C=O)ºÍϩͪ»ù(>C=C=O)¡£
In gasification reaction, CO2 is first absorbed on carbon surface. With the temperature increase, the linear structured CO2 molecular bond is stretched still being fractured. In this process, it will result in one O atom and the remaining =C=O, which react with two unsaturated bond-containing C atoms, respectively and form two groups, i.e. ketone group (>C=O) and ketene group (>C=C=O).

ÆäÖРϩͪ»ù Îȶ¨ÐԽϲÔÚ600¡æ-700¡æ¿ªÊ¼·Ö½â£»¶øÍª»ù ±È½ÏÎȶ¨£¬³¬¹ý950¡æÒÔºó ²Å·Ö½â[32]£¬²¢ÇÒ ·Ö½â ÐèÒª½Ï¸ß ÄÜÁ¿£¬ËٶȽÏÂý£¬ÊÇ×Ü·´Ó¦µÄ ÏÞÖÆÕß[30]¡£µ±Íª»ù(>C=O)»ùÍÅÐÎ³É ºó£¬ÓÉÓÚ ÑõµÄ µç¸ºÐÔ ´óÓÚ̼µÄ µç¸ºÐÔ(XO=3.5£¬XC=2.5)£¬µç×Ó »áÏò OÔ­×Ó Æ«ÒÆ£¬ÕâÑùµÄ ½á¹û ¾ÍÊǵ¼Ö ̼µã ÕóÄÚ Æ½ºâ¡¢Îȶ¨¡¢¶Ô³ÆµÄ ·Ö×Ó¹ìµÀ ŤÇú±äÐΣ¬ÌåϵÄÜÁ¿Éý¸ß ÇÒ²»Îȶ¨¡£
ketene group is of poor stability, which begins to decompose at 600¡æ-700¡æ; while ketone group is more stable, which will not be decomposed under the temperature of 950¡æ [32]. Moreover the decomposition of ketone group requires more energy and proceed more slowly, therefore ketone group is a inhibitor for the whole reaction [30]. After the successful formation of ketone group(>C=O), since the electronegativity of O is higher than that of C(XO=3.5£¬XC=2.5), the electron will shift towards O atoms, leading to internal balance and stable of carbon lattice, distortion of symmetry molecular orbital, increase and instability of system energy.


ΪÁË Î¬³Ö ֮ǰÎȶ¨µÄ ״̬£¬Ì¼Ô­×ÓÍÅ »áÁ¦Í¼ ¶á»Ø Æ«ÏòOÔ­× µç×Ó£¬½á¹û ¾ÍÐγÉÁË Ì¼ÑõÖ®¼ä »¥ÏàÀ­¶áµÄ ¶¯Ì¬¾ÖÃæ[31]¡£Õâʱºò´¦ÓÚ dsÇø ÇÒ Ò×ʧȥ ×îÍâ²ãµç×ÓµÄ Ð¿Ô­×Ó ¼ÓÈë ½øÀ´ÁË£¬ÓÉÓÚ Ì¼µÄ µç¸ºÐÔ ´óÓÚ Ð¿µÄ µç¸ºÐÔ(XC=2.5£¬XZn=1.6)£¬Õâʱ ̼ԭ×ÓÍÅ »á¶á×ß ZnÔ­× µç×Ó ÒÔ »Ö¸´µ½ Ô­À´µÄ Îȶ¨Ì¬£¬ÕâÑù OÔ­×Ó Ò²¸üÈÝÒ× ¶áÈ¡CÔ­×Ó µÄµç×Ó£¬µ¼Ö ̼¼ü¶ÏÁÑ£¬Íª»ù·Ö½â£¬CÔ­×Ó±»½âÀ룬¼Ó¿ìÁËCOµÄ²úÉú£»¶øÍª»ù ÆÆ»µºó£¬ÓÉZn¹±Ï×µÄ µç×Ó ³ÉΪ Ê£Óàµç×Ó£¬Ê£Óàµç×Ó ÓÖ»á ÖØÐ»ص½ ZnÔ­×ÓÖУ¬Íê³ÉÁË ½âÀëCÔ­×Ó µÄ´ß»¯¹ý³Ì£¬ÕâÒ²·ûºÏ µç×ÓÑ­»· ÊÚÊÜ ´ß»¯ÀíÂÛ[32]¡£
To maintain the previous stable condition, C atomic group will try to seize back the electron which has been shifted toward O atom, therefore a dynamic pulling combat between C and O atoms is resulted [31]. In this situation, Zn atom, which exists in ds zone and is likely to loss the outermost electron, joins in such combat. As the electronegativity of C atom is higher than that of Zn atom (XC=2.5£¬XZn=1.6), the C atomic group will seize the electron of Zn atom to recover to its previous stable condition, therefore the O atom is more likely to seize the election of C atom, leading to the fracture of C bond, decomposition of ketone group, dissociation of C atom, and the accelerating of CO production; on the other hand, after the damage of ketone group, the electrons contributed by Zn atom become remaining electrons, which will return to Zn atom, so that the catalytic process for dissociation of C atom is finished, which is also consistent to the electron cyclic impartation-acceptance catalytic theory[32].
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