크롬 질화물(CrN)의 합성 및 촉매특성에 관한 연구

이용진; 권혁회; Yong-Jin Lee; Heock-Hoi Kwon

Journal of the Korean Industrial and Engineering Chemistry, Vol.17, No.5, 451-457, October, 2006

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크롬 질화물(CrN)의 합성 및 촉매특성에 관한 연구

Synthesis of Chromium Nitride and Evaluation of its Catalytic Property

이용진, 권혁회 ^†

숭실대학교 환경화학공학과

Yong-Jin Lee, and Heock-Hoi Kwon^†

Department of Chemical and Environmental Engineering, Soongsil University, Seoul 156-743, Korea

E-mail:

초록

CrCl3를 NH3와 반응시켜 약 850 ℃에서 표면적이 높은 단일 상 CrN 촉매를 합성하였다. 열질량분석을 통해 고체상 화학변이가 발생하는 온도를 파악하였고 물질의 상을 XRD로 분석하였다. 합성물질의 표면적, 결정크기 등을 분석하였고 합성변수의 영향을 확인하였다. 합성된 질화물의 표면적은 12∼47 m2/g이었다. 공간속도는 표면적 증가에 약하게나마 영향을 미쳤는데 반응중간생성물의 빠른 제거가 표면적을 높이는데 기여하는 것으로 파악되었다. 승온환원반응 분석 결과 CrN은 비활성화(passivation)시 거의 산화되지 않아 수소분위기에서의 환원이 거의 일어나지 않았으며 약 700 ℃와 950 ℃ 부근에서 결정격자 중의 질소가 N2로 분해되었다. 공기분위기에서 10 K/min의 속도로 가열하면 300 ℃ 이후의 온도에서 산화가 진행되어 800 ℃ 부근에서 Cr2O3 상이 형성되기 시작하였으며 900 ℃에서도 완전히 산화되지 않았다. 부탄과 피리딘을 이용한 활성실험 결과 CrN 촉매는 탈수소반응에 선택적으로 높은 활성을 가졌으며 수첨탈질이나 수소분해반응 활성은 거의 없었다. 부탄의 탈수소반응에서 부피반응속도는 상용 촉매인 Pt-Sn/Al2O3보다 우수하였다.

We synthesized phase pure CrN having surface areas up to 47 m2/g starting from CrCl3 with NH3. Thermal Gravimetric Analysis coupled with X-ray diffraction was carried out to identify solid state transition temperatures and the phase after each transition. In addition, the BET surface areas, pore size distributions, and crystalline diameters for the synthesized materials were analyzed. Space velocity influenced a little to the surface areas of the prepared materials, while heating rate did not. We believe it is due to the fast removal of reaction by-products from the system. Temperature programmed reduction results revealed that the CrN was hardly passivated by 1% O2. Molecular nitrogen was detected from CrN at 700 and 950 ℃, which may be from lattice nitrogen. In temperature programmed oxidation with heating rate of 10 K/min in flowing air, oxidation started at or higher than 300 ℃ and resulting Cr2O3 phase was observed with XRD at around 800 ℃. However the oxidation was not completed even at 900 ℃. CrN catalysts were highly active for n-butane dehydrogenation reaction. Their activity is even higher than that of a commercial Pt-Sn/Al2O3 dehydrogenation catalyst in terms of volumetric reaction rate. However, CrN was not active in pyridine hydrodenitrogenation.

Keywords:CrN;temperature programmed reaction;butane dehydrogenation;metal nitride

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Subramanya Herle P, Hegde MS, Vasathacharya NY, Philip S, Rama Rao MV, Sripathi T, J. Solid State Chem., 134, 120 (1997)

[Related Articles]

[1] Chen JG, Fruhberger B, Weisel MD, Baumgartner JE, DeVries BD, in The Chemistry of Transition Metal Carbides and Nitrides, ed. S.T. Oyama, Blackie Academia and Professional, Glasgow (1996)

[2] Curry KE, Ph. D. Dissertation, The University of Michigan, Ann Arbor, USA (1995)

[3] Neylon MK, Choi S, Kwon H, Curry KE, Thompson LT, Appl. Catal. A: Gen., 183(2), 253 (1999)

[4] Levy RB, Boudart M, Science, 181, 547 (1973)

[5] Choi J, Brenner JR, Colling CW, Demczyk BG, Dunning J, Thompson LT, Catal. Today, 15, 201 (1992)

[6] Sajkowski DJ, Oyama ST, ACS Prep., Div. Petrol. Chem., 35, 233 (1990)

[7] Schlatter JC, Oyama ST, Metcalfe JE, Lambert JM, Ind. Eng. Chem. Res., 27, 1648 (1988)

[8] Leclerq L, Imura K, Yoshida S, Barbee T, Boudart M, in Preparation of Catalysts II, ed. B. Delmon, p. 627, Elsevier, New York (1979)

[9] Volpe L, Boudart M, J. Phys. Chem., 90, 4874 (1986)

[10] Markel EJ, Van Zee JW, J. Catal., 126, 643 (1990)

[11] Dhandapani B, Ramanathan S, Yu CC, Fruhberger B, Chen JG, Oyama ST, J. Catal., 176(1), 61 (1998)

[12] Kwon H, Choi S, Thompson LT, J. Catal., 184, 236 (2000)

[13] Kwon H, Thompson LT, Eng J, Chen JG, J. Catal., 190(1), 60 (2000)

[14] Choi JG, Brenner JR, Thompson LT, J. Catal., 154(1), 33 (1995)

[15] Oyama ST, Catal. Today, 15, 179 (1992)

[16] Milosev I, Strehblow HH, Navinsek B, Thin Solid Films, 303(1-2), 246 (1997)

[17] Hirai M, Ueno Y, Suzuki T, Jiang W, Jpn. J. Appl. Phys., 40, 1052 (2001)

[18] Japan Patent JP 02221126 (1989)

[19] Sato T, Usuki K. Okuwaki A, Goto Y, J. Mater. Sci., 27, 3879 (1992)

[20] Aguas M, Nartowski A, Parkin I, MacKensi M, Craven A, J. Mater. Chem., 8, 1875 (1998)

[21] Subramanya Herle P, Hegde M, Vasathacharya N, Philip S, J. Solid State Chem., 134, 120 (1997)

[22] Kwon H, Ph. D. Dissertation, The University of Michigan, Ann Arbor, USA (1998)

[23] Kapoor R, Oyama ST, J. Solid State Chem., 99, 303 (1992)

[24] Mulfinger HO, J. Am. Ceram. Soc., 49, 462 (1966)

[25] Brinker CJ, J. Am. Ceram. Soc., 65, C4 (1982)

[26] Subramanya Herle P, Hegde MS, Vasathacharya NY, Philip S, Rama Rao MV, Sripathi T, J. Solid State Chem., 134, 120 (1997)