1.中国科学院广州能源研究所,中国科学院可再生能源重点实验室,广东 广州 510640
2.中国科学技术大学 纳米科学技术学院,江苏 苏州 215123
王鲁丰(1994—),男,硕士研究生,wlufeng@mail.ustc.edu.cn
邓丽芳(1982—),女,博士,副研究员,denglf@ms.giec.ac.cn
收稿:2019-04-01,
修回:2019-06-25,
网络首发:2026-07-24,
纸质出版:2019-08-05
移动端阅览
王鲁丰, 钱鑫, 邓丽芳, 袁浩然. 氮气电化学合成氨催化剂研究进展[J]. 化工学报, 2019, 70(8): 2854-2863
WANG Lufeng, QIAN Xin, DENG Lifang, YUAN Haoran. Recent progress on catalysts about electrochemical synthesis of ammonia from nitrogen[J]. CIESC Journal, 2019, 70(8): 2854-2863
王鲁丰, 钱鑫, 邓丽芳, 袁浩然. 氮气电化学合成氨催化剂研究进展[J]. 化工学报, 2019, 70(8): 2854-2863 DOI: 10.11949/0438-1157.20190308.
WANG Lufeng, QIAN Xin, DENG Lifang, YUAN Haoran. Recent progress on catalysts about electrochemical synthesis of ammonia from nitrogen[J]. CIESC Journal, 2019, 70(8): 2854-2863 DOI: 10.11949/0438-1157.20190308.
氮气是储量丰富且廉价易得的氮源,但无法被人类或动植物直接吸收利用,只有通过化学或生物方法将空气中游离的氮气转化为含氮化合物才能被人类应用于食品或其他工业生产中,因此氮气的固定及转化已经逐渐成为新的研究热点。而氨是一种非常重要的无机化工产品,其在农业、医药、储能等行业中有着重要的作用,且需求量随着社会日益发展和人口的不断增加而不断增加。首先简单介绍了现有的氮气固定合成氨方法及其作用机理,随后重点综述了氮气电化学合成氨催化剂的研究现状,最后对氮气电化学合成氨催化剂的未来发展趋势进行了展望。
Nitrogen (N
2
) is an important component of atmosphere
so human
animal or plant cannot used or absorbed it directly
and then it is necessary of converting N
2
to nitrogen-containing compounds that can be used in human food and other industrial production. Therefore
the fixation and conversion of nitrogen has gradually become a new research hotspot. Ammonia is a very important inorganic chemical product
which plays an important role in agriculture
medicine
energy storage and other industries
and the demand is increasing with the development of society and the increasing population. The existing nitrogen-fixed ammonia synthesis method and its mechanism are briefly introduced. Then the research status of nitrogen electrochemical synthesis ammonia catalyst is reviewed. Finally
the future devel
opment trend of nitrogen electrochemical synthesis ammonia catalyst is prospected.
Jia H P , Quadrelli E A . Mechanistic aspects of dinitrogen cleavage and hydrogenation to produce ammonia in catalysis and organometallic chemistry: relevance of metal hydride bonds and dihydrogen [J ] . Chemical Society Reviews , 2014 , 43 ( 2 ): 547 - 564 .
Kim J , Rees D C . Structural models for the metal centers in the nitrogenase molybdenum-iron protein [J ] . Science , 1992 , 257 ( 5077 ): 1677 - 1682 .
Eady R R . Structure-function relationships of alternative nitrogenases [J ] . Chemical Reviews , 1996 , 96 ( 7 ): 3013 - 3030 .
Howard J B , Rees D C . Structural basis of biological nitrogen fixation [J ] . Chemical Reviews , 1996 , 96 ( 7 ): 2965 - 2982 .
肖瑶 , 胡文娟 , 任衍彪 , 等 . 仿生光电催化 [J ] . 化学进展 , 2018 , 30 ( 4 ): 325 - 337 .
Xiao Y , Hu W J , Ren Y B , et al . Bioinspired photo/electrocatalytic N 2 fixation [J ] . Progress in Chemsitry , 2018 , 30 ( 4 ): 325 - 337 .
Klerke A , Christensen H C , Nørskov J K , et al . Ammonia for hydrogen storage:challenges and opportunities [J ] . Journal of Materials Chemistry , 2008 , 18 ( 20 ): 2304 - 2310 .
Zamfirescu C , Dincer I . Using ammonia as a sustainable fuel [J ] . Journal of Power Sources , 2008 , 185 ( 1 ): 459 - 465 .
Montoya J H , Tsai C , Vojvodic A , et al . The challenge of electrochemical ammonia synthesis:a new perspective on the role of nitrogen scaling relations [J ] . ChemSusChem , 2015 , 8 ( 13 ): 2180 - 2186 .
Chen J G , Crooks R M , Seefeldt L C , et al . Beyond fossil fuel-driven nitrogen transformations [J ] . Science , 2018 , 360 ( 6391 ): eaar6611
Sclafani A , Augugliaro V , Schiavello M . Dinitrogen electrochemical reduction to ammonia over iron cathode in aqueous medium [J ] . Journal of the Electrochemical Society 1983 , 130 ( 3 ): 734 - 736 .
Marnellos G , Stoukides M . Ammonia synthesis at atmospheric pressure [J ] . Science , 1998 , 282 ( 5386 ): 98 - 100 .
Murakami T , Nohira T , Goto T , et al . Electrolytic ammonia synthesis from water and nitrogen gas in molten salt under atmospheric pressure [J ] . Electrochimica Acta , 2005 , 50 ( 27 ): 5423 - 5426 .
Kumar D , Pal S , Krishnamurty S . N 2 activation on Al metal clusters: catalyzing role of BN-doped graphene support [J ] . Physical Chemistry Chemical Physics , 2016 , 18 ( 40 ): 27721 - 27727 .
Shilov A E . Catalytic reduction of molecular nitrogen in solutions [J ] . Russian Chemical Bulletin , 2003 , 52 ( 12 ): 2555 - 2562 .
Zhang S Y , Zhang X Y , Zhang Z S , et al . Electroreduction behavior of dinitrogen over ruthenium cathodic catalyst [J ] . Chemistry Letters , 2003 , 32 ( 5 ): 440 - 441 .
Ham C J M V D , Koper M T M , Hetterscheid D G . Challenges in reduction of dinitrogen by proton and electron transfer [J ] . Chemical Society Reviews , 2014 , 43 ( 15 ): 5183 - 5191 .
Shipman M A , Symes M D . Recent progress towards the electrosynthesis of ammonia from sustainable resources [J ] . Catalysis Today , 2017 , 286 : 57 - 68 .
Li M Q , Huang H , Low J X , et al . Recent progress on electrocatalyst and photocatalyst design for nitrogen reduction [J ] . Small Methods , 2018 , 1800388 .
Skulason E , Bligaard T , Gudmundsdottir S , et al . A theoretical evaluation of possible transition metal electro-catalysts for N 2 reduction [J ] . Physical Chemistry Chemical Physics , 2012 , 14 ( 3 ): 1235 - 1245 .
Zhao Y X , Zhao Y F , Shi R , et al . Tuning oxygen vacancies in ultrathin TiO 2 nanosheets to boost photocatalytic nitrogen fixation up to 700 nm [J ] . Advanced Materials , 2019 , 31 ( 16 ): e1806482 .
Abghoui Y , Skúlason E . Computational predictions of catalytic activity of zincblende (110) surfaces of metal nitrides for electrochemical ammonia synthesis [J ] . The Journal of Physical Chemistry C , 2017 , 121 ( 11 ): 6141 - 6151 .
Kordali V , Kyriacou G , Lambrou C . Electrochemical synthesis of ammonia at atmospheric pressure and low temperature in a solid polymer electrolyte cell [J ] . Chemical Communications , 2000 , 17 : 1673 - 1674 .
Ren X , Zhao J X , Wei Q , et al . High-performance N 2 -to-NH 3 conversion electrocatalyzed by Mo 2 C nanorod [J ] . ACS Central Science , 2019 , 5 ( 1 ): 116 - 121 .
Sheets B L , Botte G G . Electrochemical nitrogen reduction to ammonia under mild conditions enabled by a polymer gel electrolyte [J ] . Chemical Communications , 2018 , 54 ( 34 ): 4250 - 4253 .
Bao D , Zhang Q , Meng F L , et al . Electrochemical reduction of N 2 under ambient conditions for artificial N 2 fixation and renewable energy storage using N 2 /NH 3 cycle [J ] . Advanced Materials , 2017 , 29 ( 3 ): 1604799 .
Shi M M , Bao D , Wulan B R , et al . Au sub-nanoclusters on TiO 2 toward highly efficient and selective electrocatalyst for N 2 conversion to NH 3 at ambient conditions [J ] . Advanced Materials , 2017 , 29 ( 17 ): 1606550 .
Qin Q , Heil T , Antonietti M , et al . Single‐site gold catalysts on hierarchical N-doped porous noble carbon for enhanced electrochemical reduction of nitrogen [J ] . Small Methods , 2018 , 2 ( 12 ): 1800202 .
Zhu X J , Liu Z C , Wang H B , et al . Boosting electrocatalytic N 2 reduction to NH 3 on beta-FeOOH by fluorine doping [J ] . Chemical Communications , 2019 , 55 ( 27 ): 3987 - 3990 .
Chen H Y , Zhu X J , Huang H , et al . Sulfur dots-graphene nanohybrid: a metal-free electrocatalyst for efficient N 2 -to-NH 3 fixation under ambient conditions [J ] . Chemical Communications , 2019 , 55 ( 21 ): 3152 - 3155 .
Huang H , Xia L , Cao R R , et al . A biomass-derived carbon-based electrocatalyst for efficient N 2 fixation to NH 3 under ambient conditions [J ] . Chemistry-A European Journal , 2019 , 25 ( 8 ): 1914 - 1917 .
Wang Z , Gong F , Zhang L , et al . Electrocatalytic hydrogenation of N 2 to NH 3 by MnO: experimental and theoretical investigations [J ] . Advanced Science , 2019 , 6 ( 1 ): 1801182 .
Xia L , Li B B , Zhang Y , et al . Cr 2 O 3 nanoparticle-reduced graphene oxide hybrid: a highly active electrocatalyst for N 2 reduction at ambient conditions [J ] . Inorganic Chemistry , 2019 , 58 ( 4 ): 2257 - 2260 .
Zhang L L , Ding L X , Chen G F , et al . Ammonia synthesis under ambient conditions: selective electroreduction of dinitrogen to ammonia on black phosphorus nanosheets [J ] . Angewandte Chemie , 2019 , 58 ( 9 ): 2612 - 2616 .
Nash J , Yang X , Anibal J , et al . Electrochemical nitrogen reduction reaction on noble metal catalysts in proton and hydroxide exchange membrane electrolyzers [J ] . Journal of the Electrochemical Society , 2017 , 164 ( 14 ): F1712 -F 1716 .
Wang J , Yu L , Hu L , et al . Ambient ammonia synthesis via palladium-catalyzed electrohydrogenation of dinitrogen at low overpotential [J ] . Nature Communications , 2018 , 9 ( 1 ): 1795 .
Lan R , Irvine J T S , Tao S W . Synthesis of ammonia directly from air and water at ambient temperature and pressure [J ] . Scientific Reports , 2013 , 3 : 1145 .
Brown K A , Harris D F , Wilker M B , et al . Light-driven dinitrogen reduction catalyzed by a CdSn itrogenase MoFe protein biohybrid [J ] . Bioinorganic Chemistry , 2016 , 352 ( 6284 ): 448 - 451 .
Yao Y , Zhu S Q , Wang H J , et al . A spectroscopic study on the nitrogen electrochemical reduction reaction on gold and platinum surfaces [J ] . Journal of the American Chemical Society , 2018 , 140 ( 4 ): 1496 - 1501 .
Wang Z Q , Li Y H , Yu H J , et al . Ambient electrochemical synthesis of ammonia from nitrogen and water catalyzed by flower-like gold microstructures [J ] . ChemSusChem , 2018 , 11 ( 19 ): 3480 - 3485 .
Jiang H L , Liu B , Lan Y Q , et al . From metal-organic framework to nanoporous carbon: toward a very high surface area and hydrogen uptake [J ] . Journal of the American Chemical Society , 2011 , 133 ( 31 ): 11854 - 11857 .
Shen K , Chen X D , Chen J Y , et al . Development of MOF-derived carbon-based nanomaterials for efficient catalysis [J ] . ACS Catalysis , 2016 , 6 ( 9 ): 5887 - 5903 .
Wu G , Santandreu A , Kellogg W , et al . Carbon nanocomposite catalysts for oxygen reduction and evolution reactions: from nitrogen doping to transition-metal addition [J ] . Nano Energy , 2016 , 29 (S 1 ): 83 - 110 .
Zhang H G , Osgood H , Xie X H , et al . Engineering nanostructures of PGM-free oxygen-reduction catalysts using metal-organic frameworks [J ] . Nano Energy , 2017 , 31 : 331 - 350 .
Zhao X R , Yin F X , Liu N , et al . Highly efficient metal-organic-framework catalysts for electrochemical synthesis of ammonia from N 2 (air) and water at low temperature and ambient pressure [J ] . Journal of Materials Science , 2017 , 52 ( 17 ): 10175 - 10185 .
Lee H K , Koh C S L , Lee Y H , et al . Favoring the unfavored: selective electrochemical nitrogen fixation using a reticular chemistry approach [J ] . Science Advances , 2018 , 4 ( 3 ): 3208 - 3216 .
Geng Z G , Liu Y , Kong X D , et al . Achieving a record-high yield rate of 120.9 <math id="M1"><mi mathvariant="normal">μ</mi><msub><mrow><mi mathvariant="normal">g</mi></mrow><mrow><mi>N</mi><msub><mrow><mi>H</mi></mrow><mrow><mn mathvariant="normal">3</mn></mrow></msub></mrow></msub></math> https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113943189&type= https://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=113943210&type= 6.77333355 3.55599999 ·mg cat. -1 ·h -1 for N 2 electrochemical reduction over Ru single-atom catalysts [J ] . Advanced Materials , 2018 , 30 ( 40 ): e1803498 .
Macleod K C , Holland P L . Recent developments in the homogeneous reduction of dinitrogen by molybdenum and iron [J ] . Nature Chemistry , 2013 , 5 ( 7 ): 559 - 565 .
Bhattacharya P , Prokopchuk D E , Mock M T . Exploring the role of pendant amines in transition metal complexes for the reduction of N 2 to hydrazine and ammonia [J ] . Coordination Chemistry Reviews , 2017 , 334 (S 1 ): 67 - 83 .
Ren X , Cui G W , Chen L , et al . Electrochemical N 2 fixation to NH 3 under a mbient conditions: Mo 2 N nanorod as a highly efficient and selective catalyst [J ] . Chemical Communications , 2018 , 54 ( 61 ): 8474 - 8477 .
Eizawa A , Arashiba K , Tanaka H , et al . Remarkable catalytic activity of dinitrogen-bridged dimolybdenum complexes bearing NHC-based PCP-pincer ligands toward nitrogen fixation [J ] . Nature Communications , 2017 , 8 : 14874 .
Han J R , Ji X Q , Ren X , et al . MoO 3 nanosheets for efficient electrocatalytic N 2 fixation to NH 3 [J ] . Journal of Materials Chemistry A , 2018 , 6 ( 27 ): 12974 - 12977 .
Zhang L , Ji X Q , Ren X , et al . Efficient electrochemical N 2 reduction to NH 3 on MoN nanosheets array under ambient conditions [J ] . ACS Sustainable Chemistry & Engineering , 2018 , 6 ( 8 ): 9550 - 9554 .
Yang D S , Chen T , Wang Z J . Electrochemical reduction of aqueous N 2 electrochemical reduction at low overpotential on (110)-oriented Mo nanofilm [J ] . Journal of Materials Chemistry A , 2017 , 5 ( 36 ): 18967 - 18971 .
Li X H , Li T S , Ma Y J , et al . Boosted electrocatalytic N 2 reduction to NH 3 by defect-rich MoS 2 nano flower [J ] . Advanced Energy Materials , 2018 , 8 ( 30 ): 1801357 .
Cheng H , Ding L X , Chen G F , et al . Molybdenum carbide nanodots enable efficient electrocatalytic nitrogen fixation under ambient conditions [J ] . Advanced Materials , 2018 , 30 ( 46 ): 1803694 .
Renner J N , Greenlee L F , Ayres K E , et al . Electrochemical synthesis of ammonia: a low pressure, low temperature approach [J ] . The Electrochemical Society Interface , 2015 , 24 ( 2 ): 51 - 57 .
Chen S M , Perathoner S , Ampelli C , et al . Electrocatalytic synthesis of ammonia at room temperature and atmospheric pressure from water and nitrogen on a carbon-nanotube-based electrocatalyst [J ] . Angewandte Chemie International Edition , 2017 , 56 ( 10 ): 2699 - 2703 .
Zhao X H , Lan X , Yu D K , et al . Deep eutectic-solvothermal synthesis of nanostructured Fe 3 S 4 for electrochemical N 2 fixation under ambient conditions [J ] . Chemical Communications , 2018 , 54 ( 92 ): 13010 - 13013 .
Luo Y R , Chen G F , Ding L , et al . Efficient electrocatalytic N 2 fixation with MXene under ambient conditions [J ] . Joule , 2019 , 3 ( 1 ): 279 - 289 .
Li S , Tuo P , Xie J F , et al . Ultrathin MXene nanosheets with rich fluorine termination groups realizing efficient electrocatalytic hydrogen evolution [J ] . Nano Energy , 2018 , 47 : 512 - 518 .
Azofra L M , Li N , MacFarlane D R , et al . Promising prospects for 2D d 2 –d 4 M 3 C 2 transition metal carbides (MXenes) in N 2 capture and conversion into ammonia [J ] . Energy & Environmental Science , 2016 , 9 ( 8 ): 2545 - 2549 .
Zhao J X , Zhang L , Xie X Y , et al . Ti 3 C 2 T x (T = F, OH) MXene nanosheets: conductive 2D catalysts for ambient electrohydrogenation of N 2 to NH 3 [J ] . Journal of Materials Chemistry A , 2018 , 6 ( 47 ): 24031 - 24035 .
Zhang L L , Xiao J , Wang H Y , et al . Carbon-based electrocatalysts for hydrogen and oxygen evolution reactions [J ] . ACS Catalysis , 2017 , 7 ( 11 ): 7855 - 7865 .
Chen G F , Cao X R , Wu S Q , et al . Ammonia electrosynthesis with high selectivity under ambient conditions via a Li + incorporation strategy [J ] . Journal of the American Chemical Society , 2017 , 139 ( 29 ): 9771 - 9774 .
Shinde S S , Sami A , Lee J H . Electrocatalytic hydrogen evolution using graphitic carbon nitride coupled with nanoporous graphene co-doped by S and Se [J ] . Journal of Materials Chemistry A , 2015 , 3 ( 24 ): 12810 - 12819 .
Zhang L L , Liu W , Dou Y B , et al . The role of transition metal and nitrogen in metal-N-C composites for hydrogen evolution reaction at universal pHs [J ] . The Journal of Physical Chemistry C , 2016 , 120 ( 51 ): 29047 - 29053 .
Li R , Wei Z D , Gou X L . Nitrogen and phosphorus dual-doped graphene/carbon nanosheets as bifunctional electrocatalysts for oxygen reduction and evolution [J ] . ACS Catalysis , 2015 , 5 ( 7 ): 4133 - 4142 .
Song Y F , Chen W , Zhao C C , et al . Metal-free nitrogen-doped mesoporous carbon for electroreduction of CO 2 to ethanol [J ] . Angewandte Chemie International Edition , 2017 , 56 ( 36 ): 10840 - 10844 .
Zhao S N , Song X Z , Song S Y , et al . Highly efficient heterogeneous catalytic materials derived from metal-organic framework supports/precursors [J ] . Coordination Chemistry Reviews , 2017 , 337 : 80 - 96 .
Liu Y M , Su Y , Quan X , et al . Facile ammonia synthesis from electrocatalytic N 2 reduction under ambient conditions on N-doped porous carbon [J ] . ACS Catalysis , 2018 , 8 ( 2 ): 1186 - 1191 .
Mukherjee S , Cullen D A , Karakalos S , et al . Metal-organic f ramework-derived nitrogen-doped highly disordered carbon for electrochemical ammonia synthesis using N 2 and H 2 O in alkaline electrolytes [J ] . Nano Energy , 2018 , 48 : 217 - 226 .
Ohms D , Herzog S , Franke R , et al . Influence of metal ions on the electrocatalytic oxygen reduction of carbon materials prepared from pyrolyzed polyacrylonitrile [J ] . Journal of Power Sources , 1992 , 38 ( 3 ): 327 - 334 .
Ju W , Bagger A , Hao G P , et al . Understanding activity and selectivity of metal-nitrogen-doped carbon catalysts for electrochemical reduction of CO 2 [J ] . Nature Communications , 2017 , 8 : 944 .
Tian Y H , Hu S L , Sheng X L , et al . Non-transition-metal catalytic system for N 2 reduction to NH 3 : a density functional theory study of Al-doped graphene [J ] . The Journal of Physical Chemistry Letters , 2018 , 9 ( 3 ): 570 - 576 .
Shi M M , Bao D , Li S J , et al . Anchoring PdCu amorphous nanocluster on graphene for electrochemical reduction of N 2 to NH 3 under ambient conditions in aqueous solution [J ] . Advanced Energy Materials , 2018 , 8 ( 21 ): 1800124 .
Xia L , Yang J J , Wang H B , et al . Sulfur-doped graphene for efficient electrocatalytic N 2 -to-NH 3 fixation [J ] . Chemical Communications , 2019 , 55 ( 23 ): 3371 - 3374 .
Wu T T , Li P P , Wang H B , et al . Biomass-derived oxygen-doped hollow carbon microtubes for electrocatalytic N 2 -to-NH 3 fixation under ambient conditions [J ] . Chemical Communications , 2019 , 55 ( 18 ): 2684 - 2687 .
McEnaney J M , Singh A R , Schwalbe J A , et al . Ammonia synthesis from N 2 and H 2 O using a lithium cycling electrification strategy at atmospheric pressure [J ] . Energy & Environmental Science , 2017 , 10 ( 7 ): 1621 - 1630 .
0
浏览量
2
下载量
0
CSCD
关联资源
相关文章
相关作者
相关机构
京公网安备11010102001995号