[논문]How Rh surface breaks CO 2 molecules under ambient pressure

Kim, Jeongjin; Ha, Hyunwoo; Doh, Won Hui; Ueda, Kohei; Mase, Kazuhiko; Kondoh, Hiroshi; Mun, Bongjin Simon; Kim, Hyun You; Park, Jeong Young

doi:10.1038/s41467-020-19398-1

[해외논문] How Rh surface breaks CO 2 molecules under ambient pressure 원문보기

Nature communications, v.11 no.1 = v.11, 2020년, pp.5649 -

Kim, Jeongjin (Center for Nanomaterials and Chemical Reactions, Institute for Basic Science (IBS), Daejeon, 34141 Republic of Korea) , Ha, Hyunwoo (Department of Materials Science and Engineering, Chungnam National University, Daejeon, 34134 Republic of Korea) , Doh, Won Hui (Center for Nanomaterials and Chemical Reactions, Institute for Basic Science (IBS), Daejeon, 34141 Republic of Korea) , Ueda, Kohei (Department of Chemistry, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522 Japan) , Mase, Kazuhiko (Institute of Materials Structure Science, High Energy Accelerator Research Organization, SOKENDAI (The Graduate University for Advanced Studies), 1-1 Oho, Tsukuba, 305-0801 Japan) , Kondoh, Hiroshi (Department of Chemistry, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522 Japan) , Mun, Bongjin Simon (Department of Physics and Photon Science, School of Physics and Chemistry, Gwangju Institute of Science and Technology (GIST), Gwangju, 61005 Republic of Korea) , Kim, Hyun You (Department of Materials Science and Engineering, Chungnam National University, Daejeon, 34134 Republic of Korea) , Park, Jeong Young (C)

Abstract ▼ AI-Helper

Utilization of carbon dioxide (CO2) molecules leads to increased interest in the sustainable synthesis of methane (CH4) or methanol (CH3OH). The representative reaction intermediate consisting of a carbonyl or formate group determines yields of the fuel source during catalytic reactions. However, their selective initial surface reaction processes have been assumed without a fundamental understanding at the molecular level. Here, we report direct observations of spontaneous CO2 dissociation over the model rhodium (Rh) catalyst at 0.1 mbar CO2. The linear geometry of CO2 gas molecules turns into a chemically active bent-structure at the interface, which allows non-uniform charge transfers between chemisorbed CO2 and surface Rh atoms. By combining scanning tunneling microscopy, X-ray photoelectron spectroscopy at near-ambient pressure, and computational calculations, we reveal strong evidence for chemical bond cleavage of O‒CO* with ordered intermediates structure formation of (2 × 2)-CO on an atomically flat Rh(111) surface at room temperature.Direct observation of carbon dioxide dissociation provides an origin of catalytic conversion for industrial chemical reactions. Here, the authors reveal their molecular interactions on the rhodium catalyst at near-ambient pressure by interface science techniques and computational calculations.

참고문헌 (69)

1. Shakun JD Global warming preceded by increasing carbon dioxide concentrations during the last deglaciation Nature 2012 484 49 54 10.1038/nature10915 22481357

상세보기
2. Sperry JS The impact of rising CO 2 and acclimation on the response of US forests to global warming Proc. Natl Acad. Sci. USA 2019 116 25734 25744 10.1073/pnas.1913072116 31767760

상세보기
3. Chu S Majumdar A Opportunities and challenges for a sustainable energy future Nature 2012 488 294 303 10.1038/nature11475 22895334

상세보기
4. Rostrupnielsen JR Hansen JHB CO 2 -reforming of methane over transition metals J. Catal. 1993 144 38 49 10.1006/jcat.1993.1312

상세보기
5. Olah GA Towards oil independence through renewable methanol chemistry Angew. Chem. Int. Ed. 2013 52 104 107 10.1002/anie.201204995

상세보기
6. Freund HJ Roberts MW Surface chemistry of carbon dioxide Surf. Sci. Rep. 1996 25 225 273 10.1016/S0167-5729(96)00007-6

상세보기
7. Bradford MCJ Vannice MA CO 2 reforming of CH 4 Catal. Rev. 1999 41 1 42 10.1081/CR-100101948

상세보기
8. Kuhl KP Cave ER Abram DN Jaramillo TF New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces Energy Environ. Sci. 2012 5 7050 7059 10.1039/c2ee21234j

상세보기
9. Voiry D Shin HS Loh KP Chhowalla M Low-dimensional catalysts for hydrogen evolution and CO 2 reduction Nat. Rev. Chem. 2018 2 0105 10.1038/s41570-017-0105

상세보기
10. Behrens M The active site of methanol synthesis over Cu/ZnO/Al 2 O 3 industrial catalysts Science 2012 336 893 897 10.1126/science.1219831 22517324

상세보기
11. Kattel S Ramirez PJ Chen JG Rodriguez JA Liu P Active sites for CO 2 hydrogenation to methanol on Cu/ZnO catalysts Science 2017 355 1296 1299 10.1126/science.aal3573 28336665

상세보기
12. Kim C Energy-efficient CO 2 hydrogenation with fast response using photoexcitation of CO 2 adsorbed on metal catalysts Nat. Commun. 2018 9 3027 10.1038/s41467-018-05542-5 30072704

상세보기
13. Beuls A Methanation of CO 2 : further insight into the mechanism over Rh/γ-Al 2 O 3 catalyst Appl. Catal. B-Environ. 2012 113？114 2 10 10.1016/j.apcatb.2011.02.033

상세보기
14. Solymosi F Erdohelyi A Bansagi T Methanation of CO 2 on supported rhodium catalyst J. Catal. 1981 68 371 382 10.1016/0021-9517(81)90106-8

상세보기
15. Xu S Carter EA Theoretical insights into heterogeneous (photo)electrochemical CO 2 reduction Chem. Rev. 2019 119 6631 6669 10.1021/acs.chemrev.8b00481 30561988

상세보기
16. Sexton BA Somorjai GA The hydrogenation of CO and CO 2 over polycrystalline rhodium: correlation of surface composition, kinetics and product distributions J. Catal. 1977 46 167 189 10.1016/0021-9517(77)90198-1

상세보기
17. Weinberg WH Why CO 2 does not dissociate on Rh at low temperature Surf. Sci. Lett. 1983 128 L224 L230
18. Somorjai GA Park JY Molecular surface chemistry by metal single crystals and nanoparticles from vacuum to high pressure Chem. Soc. Rev. 2008 37 2155 2162 10.1039/b719148k 18818818

상세보기
19. Salmeron M Schlogl R Ambient pressure photoelectron spectroscopy: a new tool for surface science and nanotechnology Surf. Sci. Rep. 2008 63 169 199 10.1016/j.surfrep.2008.01.001

상세보기
20. Favaro M Subsurface oxide plays a critical role in CO 2 activation by Cu(111) surfaces to form chemisorbed CO 2 , the first step in reduction of CO 2 Proc. Natl Acad. Sci. USA 2017 114 6706 6711 28607092
21. Skafte TL Selective high-temperature CO 2 electrolysis enabled by oxidized carbon intermediates Nat. Energy 2019 4 846 855 10.1038/s41560-019-0457-4

상세보기
22. Eren B Weatherup RS Liakakos N Somorjai GA Salmeron M Dissociative carbon dioxide adsorption and morphological changes on Cu(100) and Cu(111) at ambient pressures J. Am. Chem. Soc. 2016 138 8207 8211 10.1021/jacs.6b04039 27280375

상세보기
23. Kim Y Trung TSB Yang S Kim S Lee H Mechanism of the surface hydrogen induced conversion of CO 2 to methanol at Cu(111) step sites ACS Catal. 2016 6 1037 1044 10.1021/acscatal.5b02083

상세보기
24. Roiaz M Reverse water？gas shift or Sabatier methanation on Ni(110)? Stable surface species at near-ambient pressure J. Am. Chem. Soc. 2016 138 4146 4154 10.1021/jacs.5b13366 26954458

상세보기
25. Heine C Lechner BAJ Bluhm H Salmeron M Recycling of CO 2 : probing the chemical state of the Ni(111) surface during the methanation reaction with ambient-pressure X-ray photoelectron spectroscopy J. Am. Chem. Soc. 2016 138 13246 13252 10.1021/jacs.6b06939 27599672

상세보기
26. Stempel S Baumer M Freund HJ STM studies of rhodium deposits on an ordered alumina film-resolution and tip effects Surf. Sci. 1998 402？404 424 427 10.1016/S0039-6028(97)01052-2

상세보기
27. Cernota P Rider K Yoon HA Salmeron M Somorjai G Dense structures formed by CO on Rh(111) studied by scanning tunneling microscopy Surf. Sci. 2000 445 249 255 10.1016/S0039-6028(99)01073-0

상세보기
28. Hertel T Knoesel E Wolf M Ertl G Ultrafast electron dynamics at Cu(111): response of an electron gas to optical excitation Phys. Rev. Lett. 1996 76 535 538 10.1103/PhysRevLett.76.535 10061481

상세보기
29. 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
30. Pacansky J Wahlgren U Bagus PS SCF abinitio ground state energy surfaces for CO 2 and CO 2 ？ J. Chem. Phys. 1975 62 2740 2744 10.1063/1.430807

상세보기
31. McDiarmid R Doering JP Electronic excited states of CO 2 : an electron impact investigation J. Chem. Phys. 1984 80 648 656 10.1063/1.446776

상세보기
32. Thiel PA Williams ED Yates JT Jr Weinberg WH The chemisorption of CO on Rh(111) Surf. Sci. 1979 84 54 64 10.1016/0039-6028(79)90279-6

상세보기
33. Van Hove MA Koestner RJ Frost JC Somorjai GA The structure of Rh(111)(2 × 2)-3CO from LEED intensities: Simultaneous bridge and near-top adsorption in a distorted compact hexagonal CO overlayer Surf. Sci. 1983 129 482 506 10.1016/0039-6028(83)90193-0

상세보기
34. Feng X Cerda JI Salmeron M Orientation-dependent interaction between CO 2 molecules adsorbed on Ru(0001) J. Phys. Chem. Lett. 2015 6 1780 1784 10.1021/acs.jpclett.5b00643 26263349

상세보기
35. Binnig G Garcia N Rohrer H Conductivity sensitivity of inelastic scanning tunneling microscopy Phys. Rev. B 1985 32 1336 1338 10.1103/PhysRevB.32.1336

상세보기
36. Hagman B Steps control the dissociation of CO 2 on Cu(100) J. Am. Chem. Soc. 2018 140 12974 12979 10.1021/jacs.8b07906 30226048

상세보기
37. Walsh, A. D. 466. The electronic orbitals, shapes, and spectra of polyatomic molecules. Part I. AH 2 molecules. J. Chem. Soc . 2260？2266 (1953).
38. Compton RN Reinhardt PW Cooper CD Collisional ionization of Na, K, and Cs by CO 2 , COS, and CS 2 : molecular electron affinities J. Chem. Phys. 1975 63 3821 3827 10.1063/1.431875

상세보기
39. Powell CJ NIST data resources for surface analysis by X-ray photoelectron spectroscopy and Auger electron spectroscopy J. Electron. Spectros. Relat. Phenom. 2001 114-116 1097 1102 10.1016/S0368-2048(00)00252-8

상세보기
40. Beutler A On the adsorption sites for CO on the Rh(111) single crystal surface Surf. Sci. 1997 371 381 389 10.1016/S0039-6028(96)01014-X

상세보기
41. Ueda K Isegawa K Amemiya K Mase K Kondoh H Operando NAP-XPS observation and kinetics analysis of NO reduction over Rh(111) surface: characterization of active surface and reactive species ACS Catal. 2018 8 11663 11670 10.1021/acscatal.8b03180

상세보기
42. Baraldi A Spectroscopic link between adsorption site occupation and local surface chemical reactivity Phys. Rev. Lett. 2004 93 046101 10.1103/PhysRevLett.93.046101 15323775

상세보기
43. Baraldi A Lizzit S Novello A Comelli G Rosei R Second-layer surface core-level shift on Rh(111) Phys. Rev. B 2003 67 205404 10.1103/PhysRevB.67.205404

상세보기
44. Bianchettin L Experimental and theoretical surface core level shift study of the S-Rh(100) local environment J. Phys. Chem. C 2007 111 4003 4013 10.1021/jp0677593

상세보기
45. Bianchettin L Surface core level shift: high sensitive probe to oxygen-induced reconstruction of Rh(100) J. Phys. Chem. C 2009 113 13192 13198 10.1021/jp901223d

상세보기
46. Amann P A high-pressure x-ray photoelectron spectroscopy instrument for studies of industrially relevant catalytic reactions at pressures of several bars Rev. Sci. Instrum. 2019 90 103102 10.1063/1.5109321

상세보기
47. Blyholder G Molecular orbital view of chemisorbed carbon monoxide J. Phys. Chem. 1964 68 2772 2777 10.1021/j100792a006

상세보기
48. DeLouise LA White EJ Winograd N Characterization of CO binding sites on Rh{111} and Rh{331} surfaces by XPS and LEED: comparison to EELS results Surf. Sci. 1984 147 252 262 10.1016/0039-6028(84)90179-1

상세보기
49. Wiklund M Beutler A Nyholm R Andersen JN Vibrational analysis of the C 1s photoemission spectra from pure ethylidyne and ethylidyne coadsorbed with carbon monoxide on Rh(111) Surf. Sci. 2000 461 107 117 10.1016/S0039-6028(00)00542-2

상세보기
50. Kohler L High-coverage oxygen structures on Rh(111): adsorbate repulsion and site preference is not enough Phys. Rev. Lett. 2004 93 266103 10.1103/PhysRevLett.93.266103 15697994

상세보기
51. Toyoshima R High-pressure NO-induced mixed phase on Rh(111): chemically driven replacement J. Phys. Chem. C 2015 119 3033 3039 10.1021/jp507542h

상세보기
52. Koitaya T Real-time observation of reaction processes of CO 2 on Cu(997) by ambient-pressure X-ray photoelectron spectroscopy Top. Catal. 2016 59 526 531 10.1007/s11244-015-0535-1

상세보기
53. Tang DC Hwang KS Salmeron M Somorjai GA High pressure scanning tunneling microscopy study of CO poisoning of ethylene hydrogenation on Pt(111) and Rh(111) single crystals J. Phys. Chem. B 2004 108 13300 13306 10.1021/jp036580e

상세보기
54. Brune H Wintterlin J Behm RJ Ertl G Surface migration of "hot" adatoms in the course of dissociative chemisorption of oxygen on Al(111) Phys. Rev. Lett. 1992 68 624 626 10.1103/PhysRevLett.68.624 10045948

상세보기
55. Wintterlin J Schuster R Ertl G Existence of a "hot" atom mechanism for the dissociation of O 2 on Pt(111) Phys. Rev. Lett. 1996 77 123 126 10.1103/PhysRevLett.77.123 10061787

상세보기
56. Ceyer ST New mechanisms for chemistry at surfaces Science 1990 249 133 139 10.1126/science.249.4965.133 17836965

상세보기
57. Sanville E Kenny SD Smith R Henkelman G Improved grid-based algorithm for Bader charge allocation J. Comput. Chem. 2007 28 899 908 10.1002/jcc.20575 17238168

상세보기
58. Peng G Sibener SJ Schatz GC Ceyer ST Mavrikakis M CO 2 hydrogenation to formic acid on Ni(111) J. Phys. Chem. C 2012 116 3001 3006 10.1021/jp210408x

상세보기
59. Ko J Kim B-K Han JW Density functional theory study for catalytic activation and dissociation of CO 2 on bimetallic alloy surfaces J. Phys. Chem. C 2016 120 3438 3447 10.1021/acs.jpcc.6b00221

상세보기
60. Goodman DW Peebles DE White JM CO 2 dissociation on rhodium: measurement of the specific rates on Rh(111) Surf. Sci. 1984 140 L239 L243 10.1016/0039-6028(84)90374-1

상세보기
61. Abbott HL Harrison I Activated dissociation of CO 2 on Rh(111) and CO oxidation dynamics J. Phys. Chem. C 2007 111 13137 13148 10.1021/jp073686r

상세보기
62. Liu X Sun L Deng W-Q Theoretical investigation of CO 2 adsorption and dissociation on low index surfaces of transition metals J. Phys. Chem. C 2018 122 8306 8314 10.1021/acs.jpcc.7b12660

상세보기
63. 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
64. Kresse G Furthmuller J Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Comput. Mater. 1996 6 15 50 10.1016/0927-0256(96)00008-0

상세보기
65. Kresse G Joubert D From ultrasoft pseudopotentials to the projector augmented-wave method Phys. Rev. B 1999 59 1758 1775 10.1103/PhysRevB.59.1758

상세보기
66. Hammer B Hansen LB Nørskov JK Improved adsorption energetics within density-functional theory using revised Perdew？Burke？Ernzerhof functionals Phys. Rev. B 1999 59 7413 7421 10.1103/PhysRevB.59.7413

상세보기
67. Klime？ J Michaelides A Perspective: Advances and challenges in treating van der Waals dispersion forces in density functional theory J. Chem. Phys. 2012 137 120901 10.1063/1.4754130 23020317

상세보기
68. 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
69. Henkelman G Jonsson H Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points J. Chem. Phys. 2000 113 9978 9985 10.1063/1.1323224

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