電催化水還原催化劑的研究進(jìn)展

1、電催化水還原催化劑研究進(jìn)展11/292內(nèi)容框架 研究背景 電催化水還原基本原理 金屬及合金催化劑 過渡金屬化合物催化劑 總結(jié)與展望 參考文件2/293研究背景電催化水還原催化劑Pt族金屬：儲量稀少，價格昂貴。Xiumin Li and Guoqing Guan et al. J. Mater. Chem. A, , 4, 119731; Peter C. K. Vesborg and Thomas F. Jaramillo RSC Adv., , 2, 79337947;1800: Nicholson and Carlisle3/29 電催化水還原基本原理Butler-Volmer方程： 0.

2、05V時Tafel 斜率Min Zeng and Yanguang Li. J. Mater. Chem. A, , 3, 1494214962;孫世剛等 廈門大學(xué)出版社 物理化學(xué)（下），P340-P347;4/29 電催化水還原基本原理酸性條件下：堿性條件下：Tafel 斜率118 mV per decade39 mV per decade29.5 mV per decade決速步驟Volmer reactionHeyrovsky reactionTafel reactionXiumin Li and Guoqing Guan et al. J. Mater. Chem. A, , 4, 1

3、197315/29金屬及合金催化劑降低貴金屬用量在適當(dāng)載體上覆蓋單層貴金屬原子Relationship between cost of Pt and overlayer thickness for a planar catalyst configuration.HER exchange current density (i0) as a function of Pt coverage on WC thin film.Daniel V. Esposito and Jingguang G. Chen Energy Environ. Sci., , 4, 39003912; Daniel V. Es

4、posito and and Jingguang G. Chen et al. J. Am. Chem.Soc. , 134, 30253033; Yagya N. Regmi and Brian M. Leonard et al. J. Mater. Chem. A, , 3, 1008510091;Pt, Pd, or Au on WC, W2C or Mo2C.0.5M H2SO40.1M HClO46/29金屬及合金催化劑降低貴金屬用量貴金屬與其它過渡金屬形成合金Computational high-throughput screening for |GH| on 256 pure m

5、etals and surface alloys. The rows indicate the identity of the pure metal substrates, and the columns indicate the identity of the solute embedded in the surface layer of the substrate.Hydrogen evolution after each stage of BiPt surface alloy synthesis on a fluorine-doped tin-oxide substrate. (1) P

6、t film after deposition and anneal (2) immediately after Bi UPD (3) after second anneal to form the BiPt surface alloy. The inset represents a control samplePt film without Biafter first and second anneals. Current densities are normalized to the surface area of the initial, pure Pt sample, determin

7、ed by H UPD.Jeff Greeley and Jens K. Norskov et al. Nat. Mater. , 5, 909-913;穩(wěn)定性篩選：穩(wěn)定化自由能7/29金屬及合金催化劑過渡金屬替換堿性條件下水還原用Ni,不足：催化活性不夠高，逐步失活。I. Arul Raj and K. I. Vasu J. Appl. Electrochem., 1990, 20, 3238; I. A. Raj and K. I. Vasu, J. Appl. Electrochem., 1992, 22, 471477; J. R. McKone, B. F. Sadtler, C.

8、A. Werlang, N. S. Lewis and H. B. Gray, ACS Catal., , 3, 166169;Ni-Mo-Fe: long term stability and tolerance to electrochemical corrosionNi-Mo nanopowders：10mA*cm-2 320 mV11/29 過渡金屬硫族化物B. Hinnemann and J. K. Norskov et al. J. Am. Chem. Soc., , 127, 53085309; T. F. Jaramillo and I. Chorkendorff et al.

9、 Science, , 317, 100102 底面無活性，唯硫化鉬邊是HER活性位12/29 過渡金屬硫族化物介孔氧化硅模板：雙螺旋二十四面體10mA/cm2 =150-200 mV制造盡可能多邊位以邊為終端豎直排列MoS2膜j0 = 2.2*10-6 A/cm2,TOF=0.013 S-1GO穩(wěn)定納米MoS2onset =100 mV,穩(wěn)定性好硫脲加入：更多缺點J. Kibsgaard and T. F. Jaramillo et al. Nat. Mater., , 11, 963969; D. S. Kong and Y. Cui et al. Nano Lett., , 13, 13

10、411347; Y. G. Li and J. Dai et al. J. Am. Chem. Soc., , 133, 72967299; J. F. Xie and Yi Xie et al. Adv. Mater., , 25, 58075813;13/29 過渡金屬硫族化物層狀結(jié)構(gòu): WS2, MoSe2, WSe2, MoS2(1x)Se2x;硫鐵礦結(jié)構(gòu)：MX2: M = Fe, Co, Ni; X = S, Se;Fengmei Wang and Jun He et al. Nanoscale, , 7, 1976419788; H. Zhang and X. Sun et al.

11、 J. Mater. Chem. A, , 3, 63066310;Desheng Kong and Yi Cui et al. Energy Environ. Sci., , 6, 35533558;onset=61 mV,酸堿都穩(wěn)定。第一周期過渡金屬硫族化物14/29 過渡金屬碳化物和氮化物WC, W2C, and Mo2C：類貴金屬（Pt）性質(zhì)。S. T. Hunt and Y. Roman-Leshkov et al. Angew. Chem., Int. Ed., , 53, 51315136;W. F. Chen and R. R. Adzic et al. Angew. Chem

12、., Int. Ed., , 51, 61316135;MoN, Mo2N, NiMoNx/C15/29 過渡金屬磷化物(Fe, Co, Ni, Cu, Mo, W)xP： 當(dāng)前非貴金屬基最高效水還原催化劑之一。P存在降低了活潑Ni位點，形成適中鍵合能力Ping Liu and Jose A. Rodriguez J. Am. Chem. Soc. , 127, 14871-14878；16/29 過渡金屬磷化物三辛基磷(TOP)加熱到320作為磷源。E. J. Popczun and R. E. Schaak et al. J. Am. Chem. Soc., , 135, 92679270

13、; E. J. Popczun and R. E. Schaak et al. Angew. Chem., Int. Ed., , 53, 54275430; J. M. McEnaney and R. E. Schaak et al. Chem. Mater., , 26, 48264831; J. M. McEnaney and R. E. Schaak et al. Chem. Commun., , 50, 1102611028;CoP 活性更加好，二者在堿性中活性都快速衰減Ni2P:20 mA/cm2 =130 mVCoP:20 mA/cm2 =85 mVMoP:10 mA/cm2 =

14、90 mVWP:10 mA/cm2 =120 mV17/29 過渡金屬磷化物J. Q. Tian and X. P. Sun et al. J. Am. Chem. Soc., , 136, 75877590; P. Jiang and X. P. Sun et al. Angew. Chem., Int. Ed., , 53, 1285512859; J. Tian and X. P. Sun et al. Angew. Chem., Int. Ed., , 53, 95779581;次亞磷酸鈉300分解作為磷源。10 mA/cm2 =67 mV擴展到FeP和Cu3P合成1.0M PBS (

15、pH 7)1.0M KOH (pH 14)pH=0-14范圍內(nèi)很好穩(wěn)定性18/29 總結(jié)與展望電催化水還原催化劑中貴金屬依然是性能最好催化劑，不過其它替換者已經(jīng)逐步縮小了差距，以過渡金屬磷化物和Ni基合金最有希望。當(dāng)前催化劑穩(wěn)定性、活性需要深入提升，同時其制備過程安全性和便利性也有待提升。大多數(shù)水還原催化劑適合用于酸性條件下，而幾乎全部水氧化催化劑都只在堿性或中性條件下有效，在耦合水還原和水氧化時會碰到挑戰(zhàn)。未來可調(diào)變?nèi)秉c、無序結(jié)構(gòu)、晶態(tài)與非晶態(tài)、雜原子摻雜等深入提升HER活性；與碳基材料雜化提升電荷傳輸效率；選擇適當(dāng)OER催化劑與HER催化劑構(gòu)建雜化體系，提升堿性條件下HER性能。實用要求：

16、onset 100 mV 10 mA/cm2 150 mV酸性電解液：過渡金屬磷化物堿性電解液：Ni基合金19/2920謝謝!20/2921參考文件Xiumin Li and Guoqing Guan et al. J. Mater. Chem. A, , 4, 119731Peter C. K. Vesborg and Thomas F. Jaramillo RSC Adv., , 2, 79337947Min Zeng and Yanguang Li. J. Mater. Chem. A, , 3, 1494214962孫世剛等 廈門大學(xué)出版社 物理化學(xué)（下），P340-P347 Dani

17、el V. Esposito and Jingguang G. Chen Energy Environ. Sci., , 4, 39003912 Daniel V. Esposito and and Jingguang G. Chen et al. J. Am. Chem.Soc. , 134, 30253033 Yagya N. Regmi and Brian M. Leonard et al. J. Mater. Chem. A, , 3, 1008510091Jeff Greeley and Jens K. Norskov et al. Nat. Mater. , 5, 909-913I

18、. Arul Raj and K. I. Vasu J. Appl. Electrochem., 1990, 20, 3238J. R. McKone, B. F. Sadtler, C. A. Werlang, N. S. Lewis and H. B. Gray, ACS Catal., , 3, 166169R. Subbaraman and N. M. Markovic et al. Science, , 334, 12561260N. Danilovic and N. M. Markovic et al. Angew. Chem. , 124, 12663 12666M. Gong,

19、 W. Zhou and H. J. Dai, Nat. Commun., , 5, 4695Fengmei Wang and Jun He et al. Nanoscale, , 7, 1976419788M. A. Lukowski and S. Jin et al. J. Am. Chem. Soc., , 135, 1027410277B. Hinnemann and J. K. Norskov et al. J. Am. Chem. Soc., , 127, 53085309T. F. Jaramillo and I. Chorkendorff et al. Science, , 3

20、17, 100102 J. Kibsgaard and T. F. Jaramillo et al. Nat. Mater., , 11, 963969 D. S. Kong and Y. Cui et al. Nano Lett., , 13, 13411347Y. G. Li and J. Dai et al. J. Am. Chem. Soc., , 133, 72967299J. F. Xie and Yi Xie et al. Adv. Mater., , 25, 58075813H. Zhang and X. Sun et al. J. Mater. Chem. A, , 3, 6

21、3066310Desheng Kong and Yi Cui et al. Energy Environ. Sci., , 6, 35533558S. T. Hunt and Y. Roman-Leshkov et al. Angew. Chem., Int. Ed., , 53, 51315136W. F. Chen and R. R. Adzic et al. Angew. Chem., Int. Ed., , 51, 61316135Ping Liu and Jose A. Rodriguez J. Am. Chem. Soc. , 127, 14871-14878E. J. Popcz

22、un and R. E. Schaak et al. J. Am. Chem. Soc., , 135, 92679270E. J. Popczun and R. E. Schaak et al. Angew. Chem., Int. Ed., , 53, 54275430J. M. McEnaney and R. E. Schaak et al. Chem. Mater., , 26, 48264831J. M. McEnaney and R. E. Schaak et al. Chem. Commun., , 50, 1102611028J. Q. Tian and X. P. Sun e

23、t al. J. Am. Chem. Soc., , 136, 75877590P. Jiang and X. P. Sun et al. Angew. Chem., Int. Ed., , 53, 1285512859J. Tian and X. P. Sun et al. Angew. Chem., Int. Ed., , 53, 9577958121/29 補充材料22/29 補充材料23/2924補充材料24/29四、化學(xué)吸附分子軌道圖把金屬-吸附質(zhì)體系作為“表面分子”，其分子軌道由金屬和吸附分子軌道組成。原子在d-金屬上化學(xué)吸附簡化軌道示意圖（a）強化學(xué)吸附鍵（b）弱化學(xué)吸附鍵（c）

24、不能成鍵，原子離開表面單原子吸附25/29雙原子分子化學(xué)吸附雙原子分子（H2）在d-金屬上化學(xué)吸附軌道示意圖1）由HOMO組合新分子軌道。2）對LUMO做相同處理。3）觀察這些軌道相對于金屬Fermi能級位置，而且找出哪一個軌道被填充及填充程度兩個規(guī)律：1、占有分子軌道和占有表面軌道之間相互作用標(biāo)準(zhǔn)上產(chǎn)生一個排斥作用。因為成鍵和反鍵化學(xué)吸附軌道二者都將使占據(jù)。然而，假如反鍵軌道落在Fermi能級軌道之上，這種排斥作用將會部分或者全部被解除（如CO在Rh金屬上5軌道相互作用）。2、產(chǎn)生成鍵軌道相互作用，它可能出現(xiàn)在Fermi能級之上或之下。因為吸附分子所參加LUMO軌道相對于分子原子間相互作用是反鍵，對應(yīng)軌道占據(jù)將造成分子解離。假如是部分占據(jù)，則對分子和表面間成鍵貢獻(xiàn)小，同時化學(xué)吸附分子內(nèi)所包括原子相互作用減弱（如CO在大多數(shù)VIII族金屬上2*軌道情況）。26/2927/29285.8 What determines the reactivity of metals Surface structure & Electronic factorsChemisorption of an atom (H as an example) can be