基于富缺陷镍铁水滑石材料的高效析氧电极(英文)
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摘要
探索低成本高效率的析氧电极对于工业电解水技术的发展至关重要.尽管镍铁水滑石已被公认为是一种高效析氧的非贵金属催化剂,但其本征活性还有待进一步提高.本研究通过将氧空位缺陷引入镍铁水滑石,设计出一种低成本高效率的析氧电极.通过精确电子结构调控,暴露更多活性位点,提高电极导电性,富缺陷镍铁水滑石电极展现出1.40 V(vs.RHE)的低起峰电位.同时,它仅需200 m V过电势就能达到10 m A cm~(-2)的电流密度,这相比未经处理的镍铁水滑石降低了48 m V.我们进一步通过密度泛函理论计算发现,氧空位缺陷的引入使Fe的价态降低,带隙减小,使得催化过程中电子更容易被激发到导带中,从而降低反应过电势并使析氧活性增强.
Exploring efficient and cost-effective electrocatalysts for oxygen evolution reaction(OER) is critical to water splitting. While nickel-iron layered double hydroxide(Ni Fe LDH) has been long recognized as a promising nonprecious electrocatalyst for OER, its intrinsic activity needs further improvement. Herein, we design a highly-efficient oxygen evolution electrode based on defective Ni Fe LDH nanoarray. By combing the merits of the modulated electronic structure, more exposed active sites, and the conductive electrode, the defective Ni Fe LDH electrocatalysts show a low onset potential of 1.40 V(vs. RHE). An overpotential of only200 m V is required for 10 m A cm~(-2), which is 48 m V lower than that of pristine Ni Fe-LDH. Density functional theory plus U(DFT+U) calculations are further employed for the origin of this OER activity enhancement. We find the introduction of oxygen vacancies leads to a lower valance state of Fe and the narrowed bandgap, which means the electrons tend to be easily excited into the conduction band, resulting in the lowered reaction overpotential and enhanced OER performance.
Exploring efficient and cost-effective electrocatalysts for oxygen evolution reaction(OER) is critical to water splitting. While nickel-iron layered double hydroxide(Ni Fe LDH) has been long recognized as a promising nonprecious electrocatalyst for OER, its intrinsic activity needs further improvement. Herein, we design a highly-efficient oxygen evolution electrode based on defective Ni Fe LDH nanoarray. By combing the merits of the modulated electronic structure, more exposed active sites, and the conductive electrode, the defective Ni Fe LDH electrocatalysts show a low onset potential of 1.40 V(vs. RHE). An overpotential of only200 m V is required for 10 m A cm~(-2), which is 48 m V lower than that of pristine Ni Fe-LDH. Density functional theory plus U(DFT+U) calculations are further employed for the origin of this OER activity enhancement. We find the introduction of oxygen vacancies leads to a lower valance state of Fe and the narrowed bandgap, which means the electrons tend to be easily excited into the conduction band, resulting in the lowered reaction overpotential and enhanced OER performance.
引文
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15 Kargar A,Yavuz S,Kim TK,et al.Solution-processed Co Fe2O4nanoparticles on 3D carbon fiber papers for durable oxygen evolution reaction.ACS Appl Mater Interfaces,2015,7:17851-17856
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27 Wang Q,O'Hare D.Recent advances in the synthesis and application of layered double hydroxide(LDH)nanosheets.Chem Rev,2012,112:4124-4155
28 Liu Z,Ma R,Osada M,et al.Synthesis,anion exchange,and delamination of Co-Al layered double hydroxide:assembly of the exfoliated nanosheet/polyanion composite films and magneto-optical studies.J Am Chem Soc,2006,128:4872-4880
29 Ma W,Ma R,Wang C,et al.A superlattice of alternately stacked Ni-Fe hydroxide nanosheets and graphene for efficient splitting of water.ACS Nano,2015,9:1977-1984
30 Hunter BM,Hieringer W,Winkler JR,et al.Effect of interlayer anions on[Ni Fe]-LDH nanosheet water oxidation activity.Energy Environ Sci,2016,9:1734-1743
31 Wang Z,Zeng S,Liu W,et al.Coupling molecularly ultrathin sheets of Ni Fe-layered double hydroxide on Ni Co2O4nanowire arrays for highly efficient overall water-splitting activity.ACS Appl Mater Interfaces,2017,9:1488-1495
32 Yu X,Zhang M,Yuan W,et al.A high-performance three-dimensional Ni-Fe layered double hydroxide/graphene electrode for water oxidation.J Mater Chem A,2015,3:6921-6928
33 Song F,Hu X.Exfoliation of layered double hydroxides for enhanced oxygen evolution catalysis.Nat Commun,2014,5:4477
34 Gong M,Li Y,Wang H,et al.An advanced Ni-Fe layered double hydroxide electrocatalyst for water oxidation.J Am Chem Soc,2013,135:8452-8455
35 Luo M,Cai Z,Wang C,et al.Phosphorus oxoanion-intercalated layered double hydroxides for high-performance oxygen evolution.Nano Res,2017,10:1732-1739
36 Jia Y,Zhang L,Gao G,et al.A heterostructure coupling of exfoliated Ni-Fe hydroxide nanosheet and defective graphene as a bifunctional electrocatalyst for overall water splitting.Adv Mater,2017,29:1700017
37 Sun Y,Gao S,Lei F,et al.Atomically-thin two-dimensional sheets for understanding active sites in catalysis.Chem Soc Rev,2015,44:623-636
38 Zuo F,Wang L,Wu T,et al.Self-doped Ti3+enhanced photocatalyst for hydrogen production under visible light.J Am Chem Soc,2010,132:11856-11857
39 Bao J,Zhang X,Fan B,et al.Ultrathin spinel-structured nanosheets rich in oxygen deficiencies for enhanced electrocatalytic water oxidation.Angew Chem Int Ed,2015,54:7399-7404
40 Xu L,Jiang Q,Xiao Z,et al.Plasma-engraved Co3O4nanosheets with oxygen vacancies and high surface area for the oxygen evolution reaction.Angew Chem Int Ed,2016,55:5277-5281
41 Liao P,Keith JA,Carter EA.Water oxidation on pure and doped hematite(0001)surfaces:prediction of Co and Ni as effective dopants for electrocatalysis.J Am Chem Soc,2012,134:13296-13309
42 Friebel D,Louie MW,Bajdich M,et al.Identification of highly active Fe sites in(Ni,Fe)OOH for electrocatalytic water splitting.JAm Chem Soc,2015,137:1305-1313
43 Chen J,Selloni A.First principles study of cobalt(hydr)oxides under electrochemical conditions.J Phys Chem C,2013,117:20002-20006
44 Dong Y,Zhang P,Kou Y,et al.A first-principles study of oxygen formation over Ni Fe-layered double hydroxides surface.Catal Lett,2015,145:1541-1548
45 Tao L,Lin CY,Dou S,et al.Creating coordinatively unsaturated metal sites in metal-organic-frameworks as efficient electrocatalysts for the oxygen evolution reaction:Insights into the active centers.Nano Energy,2017,41:417-425
46 Xiao Z,Wang Y,Huang YC,et al.Filling the oxygen vacancies in Co3O4with phosphorus:an ultra-efficient electrocatalyst for overall water splitting.Energy Environ Sci,2017,10:2563-2569
47 Wang Y,Zhou T,Jiang K,et al.Reduced mesoporous Co3O4nanowires as efficient water oxidation electrocatalysts and supercapacitor electrodes.Adv Energy Mater,2014,4:1400696
2 Walter MG,Warren EL,Mc Kone JR,et al.Solar water splitting cells.Chem Rev,2010,110:6446-6473
3 Khan SUM,Al-Shahry M,Ingler WB.Efficient photochemical water splitting by a chemically modified n-Ti O2.Science,2002,297:2243-2245
4 Kanan MW,Nocera DG.In situ formation of an oxygen-evolving catalyst in neutral water containing phosphate and Co2+.Science,2008,321:1072-1075
5 Mc Crory CCL,Jung S,Peters JC,et al.Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction.J Am Chem Soc,2013,135:16977-16987
6 Fang YH,Liu ZP.Mechanism and tafel lines of electro-oxidation of water to oxygen on Ru O2(110).J Am Chem Soc,2010,132:18214-18222
7 Lee Y,Suntivich J,May KJ,et al.Synthesis and activities of rutile Ir O2and Ru O2nanoparticles for oxygen evolution in acid and alkaline solutions.J Phys Chem Lett,2012,3:399-404
8 Reier T,Oezaslan M,Strasser P.Electrocatalytic oxygen evolution reaction(OER)on Ru,Ir,and Pt catalysts:A comparative study of nanoparticles and bulk materials.ACS Catal,2012,2:1765-1772
9 Lettenmeier P,Wang L,Golla-Schindler U,et al.Nanosized Ir Ox-Ir catalyst with relevant activity for anodes of proton exchange membrane electrolysis produced by a cost-effective procedure.Angew Chem Int Ed,2016,55:742-746
10 Zhao Y,Jia X,Waterhouse GIN,et al.Layered double hydroxide nanostructured photocatalysts for renewable energy production.Adv Energy Mater,2016,6:1501974
11 Cao R,Lee JS,Liu M,et al.Recent progress in non-precious catalysts for metal-air batteries.Adv Energy Mater,2012,2:816-829
12 Prabu M,Ketpang K,Shanmugam S.Hierarchical nanostructured Ni Co2O4as an efficient bifunctional non-precious metal catalyst for rechargeable zinc-air batteries.Nanoscale,2014,6:3173-3181
13 Cui X,Ren P,Deng D,et al.Single layer graphene encapsulating non-precious metals as high-performance electrocatalysts for water oxidation.Energy Environ Sci,2016,9:123-129
14 Liang H,Meng F,Cabán-Acevedo M,et al.Hydrothermal continuous flow synthesis and exfoliation of Ni Co layered double hydroxide nanosheets for enhanced oxygen evolution catalysis.Nano Lett,2015,15:1421-1427
15 Kargar A,Yavuz S,Kim TK,et al.Solution-processed Co Fe2O4nanoparticles on 3D carbon fiber papers for durable oxygen evolution reaction.ACS Appl Mater Interfaces,2015,7:17851-17856
16 Chen Z,Zhao H,Zhang J,et al.Ir Ni nanoparticle-decorated flower-shaped Ni Co2O4nanostructures:controllable synthesis and enhanced electrochemical activity for oxygen evolution reaction.Sci China Mater,2017,60:119-130
17 Zhang F,Shi Y,Xue T,et al.In situ electrochemically converting Fe2O3-Ni(OH)2to Ni Fe2O4-Ni OOH:a highly efficient electrocatalyst towards water oxidation.Sci China Mater,2017,60:324-334
18 Guo S,Yang Y,Liu N,et al.One-step synthesis of cobalt,nitrogencodoped carbon as nonprecious bifunctional electrocatalyst for oxygen reduction and evolution reactions.Sci Bull,2016,61:68-77
19 Zhao Y,Jia X,Chen G,et al.Ultrafine Ni O nanosheets stabilized by Ti O2from monolayer Ni Ti-LDH precursors:An active water oxidation electrocatalyst.J Am Chem Soc,2016,138:6517-6524
20 Louie MW,Bell AT.An investigation of thin-film Ni-Fe oxide catalysts for the electrochemical evolution of oxygen.J Am Chem Soc,2013,135:12329-12337
21 G?rlin M,Chernev P,Ferreira de Araújo J,et al.Oxygen evolution reaction dynamics,faradaic charge efficiency,and the active metal redox states of Ni-Fe oxide water splitting electrocatalysts.J Am Chem Soc,2016,138:5603-5614
22 Li P,Xie Q,Zheng L,et al.Topotactic reduction of layered double hydroxides for atomically thick two-dimensional non-noble-metal alloy.Nano Res,2017,10:2988-2997
23 Wang Q,Shang L,Shi R,et al.Ni Fe layered double hydroxide nanoparticles on Co,N-codoped carbon nanoframes as efficient bifunctional catalysts for rechargeable zinc-air batteries.Adv Energy Mater,2017,7:1700467
24 Liu R,Wang Y,Liu D,et al.Water-plasma-enabled exfoliation of ultrathin layered double hydroxide nanosheets with multivacancies for water oxidation.Adv Mater,2017,29:1701546
25 Wang Y,Zhang Y,Liu Z,et al.Layered double hydroxide nanosheets with multiple vacancies obtained by dry exfoliation as highly efficient oxygen evolution electrocatalysts.Angew Chem Int Ed,2017,56:5867-5871
26 Fan G,Li F,Evans DG,et al.Catalytic applications of layered double hydroxides:recent advances and perspectives.Chem Soc Rev,2014,43:7040-7066
27 Wang Q,O'Hare D.Recent advances in the synthesis and application of layered double hydroxide(LDH)nanosheets.Chem Rev,2012,112:4124-4155
28 Liu Z,Ma R,Osada M,et al.Synthesis,anion exchange,and delamination of Co-Al layered double hydroxide:assembly of the exfoliated nanosheet/polyanion composite films and magneto-optical studies.J Am Chem Soc,2006,128:4872-4880
29 Ma W,Ma R,Wang C,et al.A superlattice of alternately stacked Ni-Fe hydroxide nanosheets and graphene for efficient splitting of water.ACS Nano,2015,9:1977-1984
30 Hunter BM,Hieringer W,Winkler JR,et al.Effect of interlayer anions on[Ni Fe]-LDH nanosheet water oxidation activity.Energy Environ Sci,2016,9:1734-1743
31 Wang Z,Zeng S,Liu W,et al.Coupling molecularly ultrathin sheets of Ni Fe-layered double hydroxide on Ni Co2O4nanowire arrays for highly efficient overall water-splitting activity.ACS Appl Mater Interfaces,2017,9:1488-1495
32 Yu X,Zhang M,Yuan W,et al.A high-performance three-dimensional Ni-Fe layered double hydroxide/graphene electrode for water oxidation.J Mater Chem A,2015,3:6921-6928
33 Song F,Hu X.Exfoliation of layered double hydroxides for enhanced oxygen evolution catalysis.Nat Commun,2014,5:4477
34 Gong M,Li Y,Wang H,et al.An advanced Ni-Fe layered double hydroxide electrocatalyst for water oxidation.J Am Chem Soc,2013,135:8452-8455
35 Luo M,Cai Z,Wang C,et al.Phosphorus oxoanion-intercalated layered double hydroxides for high-performance oxygen evolution.Nano Res,2017,10:1732-1739
36 Jia Y,Zhang L,Gao G,et al.A heterostructure coupling of exfoliated Ni-Fe hydroxide nanosheet and defective graphene as a bifunctional electrocatalyst for overall water splitting.Adv Mater,2017,29:1700017
37 Sun Y,Gao S,Lei F,et al.Atomically-thin two-dimensional sheets for understanding active sites in catalysis.Chem Soc Rev,2015,44:623-636
38 Zuo F,Wang L,Wu T,et al.Self-doped Ti3+enhanced photocatalyst for hydrogen production under visible light.J Am Chem Soc,2010,132:11856-11857
39 Bao J,Zhang X,Fan B,et al.Ultrathin spinel-structured nanosheets rich in oxygen deficiencies for enhanced electrocatalytic water oxidation.Angew Chem Int Ed,2015,54:7399-7404
40 Xu L,Jiang Q,Xiao Z,et al.Plasma-engraved Co3O4nanosheets with oxygen vacancies and high surface area for the oxygen evolution reaction.Angew Chem Int Ed,2016,55:5277-5281
41 Liao P,Keith JA,Carter EA.Water oxidation on pure and doped hematite(0001)surfaces:prediction of Co and Ni as effective dopants for electrocatalysis.J Am Chem Soc,2012,134:13296-13309
42 Friebel D,Louie MW,Bajdich M,et al.Identification of highly active Fe sites in(Ni,Fe)OOH for electrocatalytic water splitting.JAm Chem Soc,2015,137:1305-1313
43 Chen J,Selloni A.First principles study of cobalt(hydr)oxides under electrochemical conditions.J Phys Chem C,2013,117:20002-20006
44 Dong Y,Zhang P,Kou Y,et al.A first-principles study of oxygen formation over Ni Fe-layered double hydroxides surface.Catal Lett,2015,145:1541-1548
45 Tao L,Lin CY,Dou S,et al.Creating coordinatively unsaturated metal sites in metal-organic-frameworks as efficient electrocatalysts for the oxygen evolution reaction:Insights into the active centers.Nano Energy,2017,41:417-425
46 Xiao Z,Wang Y,Huang YC,et al.Filling the oxygen vacancies in Co3O4with phosphorus:an ultra-efficient electrocatalyst for overall water splitting.Energy Environ Sci,2017,10:2563-2569
47 Wang Y,Zhou T,Jiang K,et al.Reduced mesoporous Co3O4nanowires as efficient water oxidation electrocatalysts and supercapacitor electrodes.Adv Energy Mater,2014,4:1400696