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我国学者在电化学合成氨领域取得进展

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发布时间：2021-08-25

来源：酯香香化学采购网

【化工仪器网科技前沿】在国家自然科学基金项目(批准号：21536005、51621001和21776099)的资助下，华南理工大学王海辉教授团队联合美国阿贡国家实验室在常温常压电化学合成氨领域取得进展。研究成果以“铜-分子催化剂直接八电子电还原硝酸盐合成氨(Electrochemical reduction of nitrate to ammonia via direct eight-electron transfer using a copper–molecular solid catalyst)”为题，于2020年7月27日发表在《自然-能源》(Nature Energy)上。论文链接：https://www.nature.com/articles/s41560-020-0654-1。

　　氨(NH3)是氮肥生产的基本原料，对国家粮食安全至关重要。近一个世纪以来，氨的规模化生产主要依赖于能量密集型且需消耗大量化石燃料的哈伯-博施(Haber-Bosch)工艺。作为一种绿色环保的替代方法，利用可持续能源驱动的电化学低温合成策略近年来引起了学者们的研究兴趣。目前，电化学合成氨的研究主要以氮气为原料，尽管经过多年的发展，其能量利用率仍然非常低，且其氨产率比Haber-Bosch工艺低2~3个数量级。除了极难活化的N≡N键外，氮气在水中的超低溶解度也是性能难以提升的关键问题之一。

　　针对以上问题，该团队提出了电驱动硝酸盐还原合成氨的策略。据统计，我国年均排放氮氧化物总量为14.5 ± 3.1百万吨，且大量存在于环境污水中，因此以NO3− 作为氮源合成氨不仅有利于降低能源消耗、减少温室气体排放，而且有助于解决环境污水的问题。在本工作中，该团队通过筛选二十多种金属材料(图2g)，开发了一种铜耦合3,4,9,10-苝四羧酸二酐(Cu-PTCDA)固体分子催化剂，可实现以较低的过电位直接八电子还原硝酸盐制备氨(图1)。相比于析氢竞争反应需要0 V(vs可逆氢电极)的起始电位，该催化剂可实现在+0.27 V(vs可逆氢电极)还原硝酸盐，从而减少因副反应而引起的电子消耗，进而提升合成氨的法拉第效率(图2a)。通过气相色谱分析，在电合成反应时，只有0.46%的电子用于析氢竞争反应。进一步的定量分析结果表明，在−0.4 ~ −0.6 V(vs可逆氢电极)的电位时，该催化剂的氨产率为400 ~ 900 μg h−1 cm−2，法拉第效率高达60 ~ 86%(图2b~c)。相比于电化学还原氮气合成氨，其产率提升一个数量级以上。结合理论计算和实验结果表明，该催化剂优异的性能主要归因于：一方面，筛选出的金属铜中心具备独特的3d电子轨道，增强了与硝酸盐2p轨道的杂化作用，从而促进催化剂与反应物之间的电子转移(图2g)；另一方面，固体分子的共轭芳香族结构可调节质子和/或电子向铜中心位点的转移以及抑制析氢反应，从而实现高效和高选择性合成氨。

　　该研究工作为常温常压下电化学合成氨和氮肥循环利用提供了新的思路。Nature Energy杂志同期在线刊登了同行学者美国阿肯色大学的劳伦·F·格林利(Lauren F. Greenlee)博士以“循环肥料(Recycling fertilizer)”为题的评论文章。文章链接：https://www.nature.com/articles/s41560-020-0670-1。该评论文章以美国的污水氮含量和化肥使用情况为例，积极评价了王海辉教授团队的新研究工作。文章指出，美国在2016年的玉米种植面积为9400万英亩，其年氮肥使用量大概为890万吨，占美国40%的氮肥年均使用量。而美国污水中每年可用的氮含量为240万吨。从这个统计数据来看，污水中的氮是非常值得重视的宝贵资源。

　　如果能通过发展有效的污水管理体系和氮转化技术，实现氮资源的循环利用，将对资源高效利用和环境保护具有重要意义。

　　图1. 铜-分子催化剂以低能垒的方式直接八电子还原NO3−制备氨(NH3)的示意图

　　a)不同电解液条件下的线性扫描曲线：纯磷酸盐缓冲液(黑色)、含硝酸盐(红色)、含亚硝酸盐(蓝色)；b)不同电位条件下的氨产率；c)不同电位条件下的法拉第效率；d)不同反应时间时的氨产率；e)不同反应时间的法拉第效率：氨(蓝色)、亚硝酸根(粉色)；f)用核磁检测和紫外检测方法分别得到的氨产率(蓝色)和法拉第效率(粉色)；g)电荷密度差异图：蓝色电子云代表电子聚集，红色电子云代表电子消逝

　　图2. 铜-分子催化剂的电催化性能以及分子固体耦合不同金属催化剂的电荷密度差异图

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[ SQL ] SELECT * FROM `yzn_poster` WHERE `cate_id` = 99 AND `p_c_id` = 52 AND `status` = 1 LIMIT 1 [ RunTime:0.000356s ]
[ SQL ] SELECT * FROM `yzn_poster` WHERE `cate_id` = 99 AND `p_c_id` = 55 AND `status` = 1 LIMIT 1 [ RunTime:0.000261s ]
[ SQL ] SHOW COLUMNS FROM `yzn_goods_property` [ RunTime:0.000706s ]
[ SQL ] SELECT `g`.`name`,`p`.`price`,`p`.`unit`,`p`.`type`,`p`.`thumb`,p.id as p_id,`p`.`value`,`p`.`is_where`,`p`.`sku_unit`,`p`.`repeat_type`,`p`.`goods_id` FROM `yzn_goods_property` `p` LEFT JOIN `yzn_goods` `g` ON `p`.`goods_id`=`g`.`id` WHERE `p`.`status` = 1 AND `p`.`is_del` = 0 AND `g`.`is_del` = 0 AND `p`.`is_where` LIKE '%1%' AND `p`.`recommend` = 1 GROUP BY `p`.`goods_id`,`p`.`repeat_type` ORDER BY `p`.`sort` DESC,`g`.`id` DESC LIMIT 0,15 [ RunTime:0.001171s ]
[ SQL ] SHOW COLUMNS FROM `yzn_goods_category` [ RunTime:0.000653s ]
[ SQL ] SELECT * FROM `yzn_goods_category` WHERE `hot_search` = 1 AND `status` = 1 ORDER BY `listorder` ASC,`id` DESC [ RunTime:0.000286s ]
[ SQL ] SELECT * FROM `yzn_goods_category` WHERE `is_show` > 0 AND `status` = 1 ORDER BY `listorder` ASC [ RunTime:0.000246s ]
[ SQL ] SELECT * FROM `yzn_goods_category` WHERE `id` IN (1,2,7,16,17,34,92,95,38) [ RunTime:0.000235s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 1 AND `status` = 1 ORDER BY `listorder` ASC,`id` DESC [ RunTime:0.000222s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 2 AND `status` = 1 ORDER BY `listorder` ASC,`id` DESC [ RunTime:0.000171s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 7 AND `status` = 1 ORDER BY `listorder` ASC,`id` DESC [ RunTime:0.000177s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 16 AND `status` = 1 ORDER BY `listorder` ASC,`id` DESC [ RunTime:0.000159s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 17 AND `status` = 1 ORDER BY `listorder` ASC,`id` DESC [ RunTime:0.000221s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` IN (34,92) AND `status` = 1 ORDER BY `listorder` ASC,`id` DESC [ RunTime:0.000209s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` IN (95,38) AND `status` = 1 ORDER BY `listorder` ASC,`id` DESC [ RunTime:0.000168s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 1 AND `status` = 1 [ RunTime:0.000141s ]
[ SQL ] SELECT * FROM `yzn_goods_category` WHERE `status` = 1 AND `id` = 1 [ RunTime:0.000183s ]
[ SQL ] SELECT `id` FROM `yzn_goods_category` WHERE `status` = 1 AND ( arrparentid like '0,1,%' ) [ RunTime:0.000168s ]
[ SQL ] SHOW COLUMNS FROM `yzn_goods` [ RunTime:0.000638s ]
[ SQL ] SELECT `g`.`name`,p.id as p_id,`p`.`price`,`p`.`type`,`p`.`thumb`,`p`.`unit`,`p`.`is_where`,`p`.`goods_id`,`p`.`repeat_type` FROM `yzn_goods` `g` LEFT JOIN `yzn_goods_property` `p` ON `p`.`goods_id`=`g`.`id` WHERE `p`.`status` = 1 AND `p`.`is_del` = 0 AND `g`.`is_del` = 0 AND `p`.`is_where` LIKE '%1%' AND `g`.`cate_id` IN (25,26,29,30,48,1) AND `p`.`hot_sale` = '1' GROUP BY `p`.`repeat_type`,`p`.`goods_id` ORDER BY `p`.`sort` DESC,`p`.`id` DESC LIMIT 0,10 [ RunTime:0.001013s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 2 AND `status` = 1 [ RunTime:0.000193s ]
[ SQL ] SELECT * FROM `yzn_goods_category` WHERE `status` = 1 AND `id` = 2 [ RunTime:0.000167s ]
[ SQL ] SELECT `id` FROM `yzn_goods_category` WHERE `status` = 1 AND ( arrparentid like '0,2,%' ) [ RunTime:0.000178s ]
[ SQL ] SELECT `g`.`name`,p.id as p_id,`p`.`price`,`p`.`type`,`p`.`thumb`,`p`.`unit`,`p`.`is_where`,`p`.`goods_id`,`p`.`repeat_type` FROM `yzn_goods` `g` LEFT JOIN `yzn_goods_property` `p` ON `p`.`goods_id`=`g`.`id` WHERE `p`.`status` = 1 AND `p`.`is_del` = 0 AND `g`.`is_del` = 0 AND `p`.`is_where` LIKE '%1%' AND `g`.`cate_id` IN (42,43,2) AND `p`.`hot_sale` = '1' GROUP BY `p`.`repeat_type`,`p`.`goods_id` ORDER BY `p`.`sort` DESC,`p`.`id` DESC LIMIT 0,10 [ RunTime:0.000912s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 7 AND `status` = 1 [ RunTime:0.000238s ]
[ SQL ] SELECT * FROM `yzn_goods_category` WHERE `status` = 1 AND `id` = 7 [ RunTime:0.000209s ]
[ SQL ] SELECT `id` FROM `yzn_goods_category` WHERE `status` = 1 AND ( arrparentid like '0,7,%' ) [ RunTime:0.000221s ]
[ SQL ] SELECT `g`.`name`,p.id as p_id,`p`.`price`,`p`.`type`,`p`.`thumb`,`p`.`unit`,`p`.`is_where`,`p`.`goods_id`,`p`.`repeat_type` FROM `yzn_goods` `g` LEFT JOIN `yzn_goods_property` `p` ON `p`.`goods_id`=`g`.`id` WHERE `p`.`status` = 1 AND `p`.`is_del` = 0 AND `g`.`is_del` = 0 AND `p`.`is_where` LIKE '%1%' AND `g`.`cate_id` IN (10,14,32,33,49,50,51,52,53,54,55,56,57,58,96,97,7) AND `p`.`hot_sale` = '1' GROUP BY `p`.`repeat_type`,`p`.`goods_id` ORDER BY `p`.`sort` DESC,`p`.`id` DESC LIMIT 0,10 [ RunTime:0.001019s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 16 AND `status` = 1 [ RunTime:0.000210s ]
[ SQL ] SELECT * FROM `yzn_goods_category` WHERE `status` = 1 AND `id` = 16 [ RunTime:0.000243s ]
[ SQL ] SELECT `id` FROM `yzn_goods_category` WHERE `status` = 1 AND ( arrparentid like '0,16,%' ) [ RunTime:0.000178s ]
[ SQL ] SELECT `g`.`name`,p.id as p_id,`p`.`price`,`p`.`type`,`p`.`thumb`,`p`.`unit`,`p`.`is_where`,`p`.`goods_id`,`p`.`repeat_type` FROM `yzn_goods` `g` LEFT JOIN `yzn_goods_property` `p` ON `p`.`goods_id`=`g`.`id` WHERE `p`.`status` = 1 AND `p`.`is_del` = 0 AND `g`.`is_del` = 0 AND `p`.`is_where` LIKE '%1%' AND `g`.`cate_id` IN (59,60,61,62,63,16) AND `p`.`hot_sale` = '1' GROUP BY `p`.`repeat_type`,`p`.`goods_id` ORDER BY `p`.`sort` DESC,`p`.`id` DESC LIMIT 0,10 [ RunTime:0.000874s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 17 AND `status` = 1 [ RunTime:0.000192s ]
[ SQL ] SELECT * FROM `yzn_goods_category` WHERE `status` = 1 AND `id` = 17 [ RunTime:0.000237s ]
[ SQL ] SELECT `id` FROM `yzn_goods_category` WHERE `status` = 1 AND ( arrparentid like '0,17,%' ) [ RunTime:0.000205s ]
[ SQL ] SELECT `g`.`name`,p.id as p_id,`p`.`price`,`p`.`type`,`p`.`thumb`,`p`.`unit`,`p`.`is_where`,`p`.`goods_id`,`p`.`repeat_type` FROM `yzn_goods` `g` LEFT JOIN `yzn_goods_property` `p` ON `p`.`goods_id`=`g`.`id` WHERE `p`.`status` = 1 AND `p`.`is_del` = 0 AND `g`.`is_del` = 0 AND `p`.`is_where` LIKE '%1%' AND `g`.`cate_id` IN (40,64,65,66,67,68,100,17) AND `p`.`hot_sale` = '1' GROUP BY `p`.`repeat_type`,`p`.`goods_id` ORDER BY `p`.`sort` DESC,`p`.`id` DESC LIMIT 0,10 [ RunTime:0.000920s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 34 AND `status` = 1 [ RunTime:0.000206s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 92 AND `status` = 1 [ RunTime:0.000223s ]
[ SQL ] SELECT * FROM `yzn_goods_category` WHERE `status` = 1 AND `id` IN (34,92) [ RunTime:0.000227s ]
[ SQL ] SELECT `id` FROM `yzn_goods_category` WHERE `status` = 1 AND ( arrparentid like '0,34,%' or arrparentid like '0,92,%' ) [ RunTime:0.000204s ]
[ SQL ] SELECT `g`.`name`,p.id as p_id,`p`.`price`,`p`.`type`,`p`.`thumb`,`p`.`unit`,`p`.`is_where`,`p`.`goods_id`,`p`.`repeat_type` FROM `yzn_goods` `g` LEFT JOIN `yzn_goods_property` `p` ON `p`.`goods_id`=`g`.`id` WHERE `p`.`status` = 1 AND `p`.`is_del` = 0 AND `g`.`is_del` = 0 AND `p`.`is_where` LIKE '%1%' AND `g`.`cate_id` IN (35,70,71,93,94,34,92) AND `p`.`hot_sale` = '1' GROUP BY `p`.`repeat_type`,`p`.`goods_id` ORDER BY `p`.`sort` DESC,`p`.`id` DESC LIMIT 0,10 [ RunTime:0.000994s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 95 AND `status` = 1 [ RunTime:0.000210s ]
[ SQL ] SELECT `id`,`catname` FROM `yzn_goods_category` WHERE `pid` = 38 AND `status` = 1 [ RunTime:0.000196s ]
[ SQL ] SELECT * FROM `yzn_goods_category` WHERE `status` = 1 AND `id` IN (95,38) [ RunTime:0.000254s ]
[ SQL ] SELECT `id` FROM `yzn_goods_category` WHERE `status` = 1 AND ( arrparentid like '0,38,%' or arrparentid like '0,95,%' ) [ RunTime:0.000210s ]
[ SQL ] SELECT `g`.`name`,p.id as p_id,`p`.`price`,`p`.`type`,`p`.`thumb`,`p`.`unit`,`p`.`is_where`,`p`.`goods_id`,`p`.`repeat_type` FROM `yzn_goods` `g` LEFT JOIN `yzn_goods_property` `p` ON `p`.`goods_id`=`g`.`id` WHERE `p`.`status` = 1 AND `p`.`is_del` = 0 AND `g`.`is_del` = 0 AND `p`.`is_where` LIKE '%1%' AND `g`.`cate_id` IN (47,74,75,76,77,78,79,80,81,82,83,99,95,38) AND `p`.`hot_sale` = '1' GROUP BY `p`.`repeat_type`,`p`.`goods_id` ORDER BY `p`.`sort` DESC,`p`.`id` DESC LIMIT 0,10 [ RunTime:0.000950s ]
[ SQL ] SHOW COLUMNS FROM `yzn_article` [ RunTime:0.000698s ]
[ SQL ] SELECT `A`.*,`AD`.*,`C`.`catname` FROM `yzn_article` `A` INNER JOIN `yzn_article_data` `AD` ON `A`.`id`=`AD`.`did` INNER JOIN `yzn_category` `C` ON `C`.`id`=`A`.`catid` WHERE `A`.`id` = 5584 AND `A`.`status` = 1 LIMIT 1 [ RunTime:0.000338s ]
[ SQL ] SHOW COLUMNS FROM `yzn_category` [ RunTime:0.000596s ]
[ SQL ] SELECT `id` FROM `yzn_category` WHERE `parentid` = 35 AND `status` = 1 [ RunTime:0.000198s ]
[ SQL ] SELECT `id` FROM `yzn_category` WHERE `parentid` IN (36,37,38,39,40,41,42) AND `status` = 1 [ RunTime:0.000190s ]
[ SQL ] SELECT `id` FROM `yzn_category` WHERE `parentid` = 43 AND `status` = 1 [ RunTime:0.000174s ]
[ SQL ] SELECT `id` FROM `yzn_category` WHERE `parentid` IN (44,45,46,47,48,49,50) AND `status` = 1 [ RunTime:0.000178s ]
[ SQL ] SELECT `id` FROM `yzn_category` WHERE `parentid` = 6 AND `status` = 1 [ RunTime:0.000196s ]
[ DB ] CONNECT:[ UseTime:0.000245s ] mysql:host=127.0.0.1;port=3306;dbname=yzncms;charset=utf8
[ SQL ] SELECT `A`.`id`,`A`.`title` FROM `yzn_article` `A` INNER JOIN `yzn_category` `C` ON `C`.`id`=`A`.`catid` WHERE `A`.`status` = 1 AND `A`.`catid` IN (35,36,37,38,39,40,41,42) ORDER BY `A`.`flag` DESC,`A`.`listorder` ASC,`A`.`updatetime` DESC [ RunTime:0.021243s ]
[ SQL ] UPDATE `yzn_article` SET `hits` = `hits` + 1 WHERE `id` = 5584 [ RunTime:0.000336s ]
[ SQL ] SELECT * FROM `yzn_poster` WHERE `cate_id` = 10 AND `p_c_id` = 41 ORDER BY `listorder` ASC LIMIT 4 [ RunTime:0.000453s ]
[ SQL ] SELECT COUNT(*) AS tp_count FROM `yzn_article` `a` INNER JOIN `yzn_category` `c` ON `a`.`catid`=`c`.`id` WHERE `catid` = 38 AND `a`.`status` = 1 [ RunTime:0.002981s ]
[ SQL ] SELECT `a`.*,`c`.`catname` FROM `yzn_article` `a` INNER JOIN `yzn_category` `c` ON `a`.`catid`=`c`.`id` WHERE `catid` = 38 AND `a`.`status` = 1 ORDER BY `flag` DESC,`listorder` ASC,`updatetime` DESC LIMIT 0,6 [ RunTime:0.005161s ]
[ SQL ] SELECT COUNT(*) AS tp_count FROM `yzn_article` `a` INNER JOIN `yzn_category` `c` ON `a`.`catid`=`c`.`id` WHERE `catid` = 37 AND `a`.`status` = 1 [ RunTime:0.002758s ]
[ SQL ] SELECT `a`.*,`c`.`catname` FROM `yzn_article` `a` INNER JOIN `yzn_category` `c` ON `a`.`catid`=`c`.`id` WHERE `catid` = 37 AND `a`.`status` = 1 ORDER BY `flag` DESC,`listorder` ASC,`updatetime` DESC LIMIT 0,6 [ RunTime:0.005183s ]