[논문]Controlling hot electron flux and catalytic selectivity with nanoscale metal-oxide interfaces

Lee, Si Woo; Kim, Jong Min; Park, Woonghyeon; Lee, Hyosun; Lee, Gyu Rac; Jung, Yousung; Jung, Yeon Sik; Park, Jeong Young

doi:10.1038/s41467-020-20293-y

[해외논문] Controlling hot electron flux and catalytic selectivity with nanoscale metal-oxide interfaces 원문보기

Nature communications, v.12 no.1, 2021년, pp.40 -

Lee, Si Woo (Center for Nanomaterials and Chemical Reactions, Institute for Basic Science (IBS), Daejeon, 34141 Republic of Korea) , Kim, Jong Min (Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, 34141 Republic of Korea) , Park, Woonghyeon (Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, 34141 Republic of Korea) , Lee, Hyosun (Center for Nanomaterials and Chemical Reactions, Institute for Basic Science (IBS), Daejeon, 34141 Republic of Korea) , Lee, Gyu Rac (Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, 34141 Republic of Korea) , Jung, Yousung (Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, 34141 Republic of Korea) , Jung, Yeon Sik (Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, 34141 Republic of Korea) , Park, Jeong Young (Center for Nanomaterials and Chemi)

Abstract ▼ AI-Helper

Interaction between metal and oxides is an important molecular-level factor that influences the selectivity of a desirable reaction. Therefore, designing a heterogeneous catalyst where metal-oxide interfaces are well-formed is important for understanding selectivity and surface electronic excitation at the interface. Here, we utilized a nanoscale catalytic Schottky diode from Pt nanowire arrays on TiO2 that forms a nanoscale Pt-TiO2 interface to determine the influence of the metal-oxide interface on catalytic selectivity, thereby affecting hot electron excitation; this demonstrated the real-time detection of hot electron flow generated under an exothermic methanol oxidation reaction. The selectivity to methyl formate and hot electron generation was obtained on nanoscale Pt nanowires/TiO2, which exhibited ~2 times higher partial oxidation selectivity and ~3 times higher chemicurrent yield compared to a diode based on Pt film. By utilizing various Pt/TiO2 nanostructures, we found that the ratio of interface to metal sites significantly affects the selectivity, thereby enhancing chemicurrent yield in methanol oxidation. Density function theory (DFT) calculations show that formation of the Pt-TiO2 interface showed that selectivity to methyl formate formation was much larger in Pt nanowire arrays than in Pt films because of the different reaction mechanism.Chemical interaction between metal and oxide supports is an important molecular-level factor that influences the catalytic selectivity of a desirable reaction. Here, using Pt nanowires/TiO2 catalytic nanodiodes, the authors investigate an enhancement of both selectivity and hot electron generation on metal-oxide interfacial sites.

참고문헌 (66)

1. Somorjai GA Frei H Park JY Advancing the frontiers in nanocatalysis, biointerfaces, and renewable energy conversion by innovations of surface techniques J. Am. Chem. Soc. 2009 131 16589 16605 10.1021/ja9061954 19919130

상세보기
2. Wodtke AM Electronically non-adiabatic influences in surface chemistry and dynamics Chem. Soc. Rev. 2016 45 3641 3657 10.1039/C6CS00078A 27152489

상세보기
3. Park JY Kim SM Lee H Nedrygailov II Hot-electron-mediated surface chemistry: toward electronic control of catalytic activity Acc. Chem. Res. 2015 48 2475 2483 10.1021/acs.accounts.5b00170 26181684

상세보기
4. Somorjai GA Park JY Molecular factors of catalytic selectivity Angew. Chem. Int. Ed. 2008 47 9212 9228 10.1002/anie.200803181

상세보기
5. Nienhaus H Electronic excitations by chemical reactions on metal surfaces Surf. Sci. Rep. 2002 45 1 78 10.1016/S0167-5729(01)00019-X

상세보기
6. Hasselbrink E How non-adiabatic are surface dynamical processes? Curr. Opin. Solid State Mater. Sci. 2006 10 192 204 10.1016/j.cossms.2007.04.003

상세보기
7. Wodtke AM Matsiev D Auerbach DJ Energy transfer and chemical dynamics at solid surfaces: the special role of charge transfer Prog. Surf. Sci. 2008 83 167 214 10.1016/j.progsurf.2008.02.001

상세보기
8. Park JY Baker LR Somorjai GA Role of hot electrons and metal？oxide interfaces in surface chemistry and catalytic reactions Chem. Rev. 2015 115 2781 2817 10.1021/cr400311p 25791926

상세보기
9. Gergen B Nienhaus H Weinberg WH McFarland EW Chemically induced electronic excitations at metal surfaces Science 2001 294 2521 2523 10.1126/science.1066134 11752571

상세보기
10. Lee H Nedrygailov II Lee C Somorjai GA Park JY Chemicalreactioninduced hot electron flows on platinum colloid nanoparticles under hydrogen oxidation: impact of nanoparticle size Angew. Chem. Int. Ed. 2015 54 2340 2344 10.1002/anie.201410951

상세보기
11. Karpov EG Nedrygailov I Nonadiabatic chemical-to-electrical energy conversion in heterojunction nanostructures Phys. Rev. B 2010 81 205443 10.1103/PhysRevB.81.205443

상세보기
12. Hashemian M Palacios E Nedrygailov I Diesing D Karpov E Thermal properties of the stationary current in mesoporous Pt/TiO 2 structures in an oxyhydrogen atmosphere ACS Appl. Mater. Interfaces 2013 5 12375 12379 10.1021/am403182v 24256205

상세보기
13. Diesing D Hasselbrink E Chemical energy dissipation at surfaces under UHV and high pressure conditions studied using metal？insulator？metal and similar devices Chem. Soc. Rev. 2016 45 3747 3755 10.1039/C5CS00932D 27186600

상세보기
14. Nienhaus H Electron-hole pair creation at Ag and Cu surfaces by adsorption of atomic hydrogen and deuterium Phys. Rev. Lett. 1999 82 446 10.1103/PhysRevLett.82.446

상세보기
15. Ro I Resasco J Christopher P Approaches for understanding and controlling interfacial effects in oxide-supported metal catalysts ACS Catal. 2018 8 7368 7387 10.1021/acscatal.8b02071

상세보기
16. Sun YN The interplay between structure and CO oxidation catalysis on metalsupported ultrathin oxide films Angew. Chem. Int. Ed. 2010 49 4418 4421 10.1002/anie.201000437

상세보기
17. Cargnello M Control of metal nanocrystal size reveals metal-support interface role for ceria catalysts Science 2013 341 771 773 10.1126/science.1240148 23868919

상세보기
18. Tauster S Fung S Garten RL Strong metal-support interactions. Group 8 noble metals supported on titanium dioxide J. Am. Chem. Soc. 1978 100 170 175 10.1021/ja00469a029

상세보기
19. Tauster S Fung S Baker R Horsley J Strong interactions in supported-metal catalysts Science 1981 211 1121 1125 10.1126/science.211.4487.1121 17755135

상세보기
20. Matsubu JC Adsorbate-mediated strong metal？support interactions in oxide-supported Rh catalysts Nat. Chem. 2017 9 120 127 10.1038/nchem.2607 28282057

상세보기
21. Green IX Tang W Neurock M Yates JT Spectroscopic observation of dual catalytic sites during oxidation of CO on a Au/TiO 2 catalyst Science 2011 333 736 739 10.1126/science.1207272 21817048

상세보기
22. Haruta M Kobayashi T Sano H Yamada N Novel gold catalysts for the oxidation of carbon monoxide at a temperature far below 0 °C Chem. Lett. 1987 16 405 408 10.1246/cl.1987.405

상세보기
23. Ye R Zhao J Wickemeyer BB Toste FD Somorjai GA Foundations and strategies of the construction of hybrid catalysts for optimized performances Nat. Catal. 2018 1 318 325 10.1038/s41929-018-0052-2

상세보기
24. Gross E Liu JH-C Toste FD Somorjai GA Control of selectivity in heterogeneous catalysis by tuning nanoparticle properties and reactor residence time Nat. Chem. 2012 4 947 952 10.1038/nchem.1465 23089871

상세보기
25. Lee I Delbecq F Morales R Albiter MA Zaera F Tuning selectivity in catalysis by controlling particle shape Nat. Mater. 2009 8 132 138 10.1038/nmat2371 19151702

상세보기
26. Wittstock A Zielasek V Biener J Friend C Baumer M Nanoporous gold catalysts for selective gas-phase oxidative coupling of methanol at low temperature Science 2010 327 319 322 10.1126/science.1183591 20075249

상세보기
27. Eren B Structure of the clean and oxygen-covered Cu (100) surface at room temperature in the presence of methanol vapor in the 10？200 mTorr pressure range J. Phys. Chem. B 2017 122 548 554 10.1021/acs.jpcb.7b04681 28749680

상세보기
28. Zugic B Dynamic restructuring drives catalytic activity on nanoporous gold？silver alloy catalysts Nat. Mater. 2017 16 558 564 10.1038/nmat4824 27992418

상세보기
29. Wang H Influence of size-induced oxidation state of platinum nanoparticles on selectivity and activity in catalytic methanol oxidation in the gas phase Nano Lett. 2013 13 2976 2979 10.1021/nl401568x 23701488

상세보기
30. Lee SW Intrinsic relation between hot electron flux and catalytic selectivity during methanol oxidation ACS Catal. 2019 9 8424 8432 10.1021/acscatal.9b02402

상세보기
31. Chen Z Understanding the dual active sites of the FeO/Pt (111) interface and reaction kinetics: density functional theory study on methanol oxidation to formaldehyde ACS Catal. 2017 7 4281 4290 10.1021/acscatal.7b00541

상세보기
32. Farnesi Camellone M Molecular understanding of reactivity and selectivity for methanol oxidation at the Au/TiO 2 interface Angew. Chem. Int. Ed. 2013 52 5780 5784 10.1002/anie.201301868

상세보기
33. Contreras A Yan X-M Kwon S Bokor J Somorjai G Catalytic CO oxidation reaction studies on lithographically fabricated platinum nanowire arrays with different oxide supports Catal. Lett. 2006 111 5 13 10.1007/s10562-006-0123-x

상세보기
34. Contreras A Grunes J Yan X-M Liddle A Somorjai G Fabrication of 2-dimensional platinum nanocatalyst arrays by electron beam lithography: ethylene hydrogenation and CO-poisoning reaction studies Top. Catal. 2006 39 123 129 10.1007/s11244-006-0047-0

상세보기
35. Kim JM Eliminating the tradeoff between the throughput and pattern quality of sub15 nm directed selfassembly via warm solvent annealing Adv. Funct. Mater. 2015 25 306 315 10.1002/adfm.201401529

상세보기
36. Jung YS Ross CA Orientation-controlled self-assembled nanolithography using a polystyrene？polydimethylsiloxane block copolymer Nano Lett. 2007 7 2046 2050 10.1021/nl070924l 17570733

상세보기
37. Goddeti KC Lee H Jeon B Park JY Enhancing hot electron collection with nanotube-based three-dimensional catalytic nanodiode under hydrogen oxidation Chem. Commun. 2018 54 8968 8971 10.1039/C8CC04288H

상세보기
38. Jeon B Lee H Goddeti KC Park JY Hot electron transport on three-dimensional Pt/mesoporous TiO 2 Schottky nanodiodes ACS Appl. Mater. Interfaces 2019 11 15152 15159 10.1021/acsami.9b02863 30939872

상세보기
39. Park JY Renzas J Hsu BB Somorjai GA Interfacial and chemical properties of Pt/TiO 2 , Pd/TiO 2 , and Pt/GaN catalytic nanodiodes influencing hot electron flow J. Phys. Chem. C 2007 111 15331 15336 10.1021/jp074562h

상세보기
40. Park JY Lee H Renzas JR Zhang Y Somorjai GA Probing hot electron flow generated on Pt nanoparticles with Au/TiO 2 Schottky diodes during catalytic CO oxidation Nano Lett. 2008 8 2388 2392 10.1021/nl8012456 18572970

상세보기
41. Lee H Graphene？semiconductor catalytic nanodiodes for quantitative detection of hot electrons induced by a chemical reaction Nano Lett. 2016 16 1650 1656 10.1021/acs.nanolett.5b04506 26910271

상세보기
42. Hervier A Baker LR Komvopoulos K Somorjai GA Titanium oxide/platinum catalysis: charge transfer from a titanium oxide support controls activity and selectivity in methanol oxidation on platinum J. Phys. Chem. C 2011 115 22960 22964 10.1021/jp2066327

상세보기
43. Yoon S Specific metal？support interactions between nanoparticle layers for catalysts with enhanced methanol oxidation activity ACS Catal. 2018 8 5394 5398 10.1021/acscatal.8b00276

상세보기
44. Xu M Insights into interfacial synergistic catalysis over Ni@TiO 2？x catalyst toward water？gas shift reaction J. Am. Chem. Soc. 2018 140 11241 11251 10.1021/jacs.8b03117 30016862

상세보기
45. Xu M TiO 2？x -modified Ni nanocatalyst with tunable metal？support interaction for water？gas shift reaction ACS Catal. 2017 7 7600 7609 10.1021/acscatal.7b01951

상세보기
46. Liu N Au δ？？O v ？Ti 3+ interfacial site: catalytic active center toward low-temperature water gas shift reaction ACS Catal. 2019 9 2707 2717 10.1021/acscatal.8b04913

상세보기
47. Hervier A Renzas JR Park JY Somorjai GA Hydrogen oxidation-driven hot electron flow detected by catalytic nanodiodes Nano Lett. 2009 9 3930 3933 10.1021/nl9023275 19731919

상세보기
48. Lee H Enhanced hot electron generation by inverse metal？oxide interfaces on catalytic nanodiode Faraday Dicuss. 2019 214 353 364 10.1039/C8FD00136G

상세보기
49. Lee H Boosting hot electron flux and catalytic activity at metal？oxide interfaces of PtCo bimetallic nanoparticles Nat. Commun. 2018 9 2235 10.1038/s41467-018-04713-8 29884825

상세보기
50. An K Enhanced CO oxidation rates at the interface of mesoporous oxides and Pt nanoparticles J. Am. Chem. Soc. 2013 135 16689 16696 10.1021/ja4088743 24090187

상세보기
51. Baker LR Furfuraldehyde hydrogenation on titanium oxide-supported platinum nanoparticles studied by sum frequency generation vibrational spectroscopy: acid？base catalysis explains the molecular origin of strong metal？support interactions J. Am. Chem. Soc. 2012 134 14208 14216 10.1021/ja306079h 22871058

상세보기
52. Hanukovich S Dang A Christopher P Influence of metal oxide support acid sites on Cu-catalyzed nonoxidative dehydrogenation of ethanol to acetaldehyde ACS Catal. 2019 9 3537 3550 10.1021/acscatal.8b05075

상세보기
53. Yang, Z. -Y., Wojtaszek-Gurdak, A., Yang, C. -M. & Ziolek, M. Enhancement of selectivity in methanol oxidation over copper containing SBA-15 by doping with boron species. Catal. Today 356 , 122？131 (2020).
54. Bunluesin T Putna E Gorte R A comparison of CO oxidation on ceria-supported Pt, Pd, and Rh Catal. Lett. 1996 41 1 5 10.1007/BF00811703

상세보기
55. Lee SW Song JT Kim J Oh J Park JY Enhanced catalytic activity for CO oxidation by the metal？oxide perimeter of TiO 2 /nanostructured Au inverse catalysts Nanoscale 2018 10 3911 3917 10.1039/C7NR08168E 29423473

상세보기
56. Qadir K Tailoring metal？oxide interfaces of inverse catalysts of TiO 2 /nanoporous-Au under hydrogen oxidation Chem. Commun. 2015 51 9620 9623 10.1039/C5CC02832A

상세보기
57. Kennedy G Melaet Grm Han H-L Ralston WT Somorjai GA In situ spectroscopic investigation into the active sites for crotonaldehyde hydrogenation at the Pt nanoparticle？Co 3 O 4 interface ACS Catal. 2016 6 7140 7147 10.1021/acscatal.6b01640

상세보기
58. Xu B Haubrich J Baker TA Kaxiras E Friend CM Theoretical study of O-assisted selective coupling of methanol on Au (111) J. Phys. Chem. C. 2011 115 3703 3708 10.1021/jp110835w

상세보기
59. Nørskov, J. K., Studt, F., Abild-Pedersen, F. & Bligaard, T. Fundamental Concepts in Heterogeneous Catalysis (Wiley, 2014).
60. Kim J Adsorbate-driven reactive interfacial Pt-NiO 1？x nanostructure formation on the Pt 3 Ni (111) alloy surface Sci. Adv. 2018 4 eaat3151 10.1126/sciadv.aat3151 30027118

상세보기
61. Kresse G Furthmuller J Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Comput. Mater. Sci. 1996 6 15 50 10.1016/0927-0256(96)00008-0

상세보기
62. Perdew JP Burke K Ernzerhof M Generalized gradient approximation made simple Phys. Rev. Lett. 1996 77 3865 10.1103/PhysRevLett.77.3865 10062328

상세보기
63. Blochl PE Projector augmented-wave method Phys. Rev. B 1994 50 17953 10.1103/PhysRevB.50.17953

상세보기
64. Dudarev S Botton G Savrasov S Humphreys C Sutton A Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA + U study Phys. Rev. B 1998 57 1505 10.1103/PhysRevB.57.1505

상세보기
65. Henkelman G Uberuaga BP Jonsson H A climbing image nudged elastic band method for finding saddle points and minimum energy paths J. Chem. Phys. 2000 113 9901 9904 10.1063/1.1329672

상세보기
66. Tang W Sanville E Henkelman G A grid-based Bader analysis algorithm without lattice bias J. Phys. Condens. Matter 2009 21 084204 10.1088/0953-8984/21/8/084204 21817356

상세보기

LOADING...

활용도 분석정보

상세보기

다운로드

내보내기

활용도 Top5 논문

해당 논문의 주제분야에서 활용도가 높은 상위 5개 콘텐츠를 보여줍니다.
더보기 버튼을 클릭하시면 더 많은 관련자료를 살펴볼 수 있습니다.

표제어: PCR

동의어: Packet Collision Rate

용어 설명 출처 목록 (6)

용어 설명: PCR은 세균 특이성이 있는 primer를 이용하여 적은 수의 세균이 있을지라도 쉽게 검출할 수 있는 유용한 방법이며, 이를 이용하여 구강 내 치면세균막이나 타액에서 직접 세균을 검출할 수 있게 되었다[8].

내보내기 구분	파일저장 인쇄 메일전송
구성항목	기본정보 상세정보 관리번호, 논문명, 저널/프로시딩명, 저자 , 발행년, 권, 호, 시작페이지, 끝페이지, 발행기관 관리번호, 논문명, 대등논문명, 저자 , 저널/프로시딩명, 발행기관, 발행년, 발행언어, 권, 호, 시작페이지, 끝페이지, ISBN, ISSN, 주제분야, 키워드, 초록(한글), 초록(영문), 저자(소속기관)
저장형식	Text(ASCII format) Excel format RefWorks Direct Export RIS format (for Reference Manager, ProCite, EndNote), Scholar's Aids, Mendeley
메일정보	받는사람 (필수) @ 보내는사람 (선택) @ 제목 내용 KISTI 검색결과 이메일 서비스
안내	총 건의 자료가 검색되었습니다. 다운받으실 자료의 인덱스를 입력하세요. (1-10,000) 검색결과의 순서대로 최대 10,000건 까지 다운로드가 가능합니다. 데이타가 많을 경우 속도가 느려질 수 있습니다.(최대 2~3분 소요) 다운로드 파일은 UTF-8 형태로 저장됩니다. 파일의 내용이 제대로 보이지 않을실 때는 웹브라우저 상단의 보기 -> 인코딩 -> 자동선택 여부를 확인하십시오. ~ Text(ASCII format) Excel format

연합인증