Pd^(1) Location and Adsorbate Interactions in PdH-SAPO-34 studied by EPR and Electron Spin-Echo Modulation Spectroscopies

Back, Gern-Ho,Yu, Jong-Sung,Vadim Kurshev,Larry Kevan 國立 昌原大學校 基礎科學硏究所 1994 基礎科學硏究所論文集 Vol.6 No.-

EPR and electron spin-echo modulation (ESEM) spectroscopies have been used to monitor the location of Pd_(II) and its interaction with water, methanol, ethanol, ethene, benzene, carbon monoxide and ammonia in silicoaluminophosiphate type 34 (SAPO-34) molecular sieve containing Pd(II) by ion exchange. After activation at 600℃, three different Pd' species are observed: A_(1)(g_(⊥) = 2.177), A_(2)(g_(⊥) = 2.136) and A_(3)(g_(⊥) = 2.070) with a common g_(Ⅱ)= 2.92. These correspond to three different site locations in the framework. A_(1) is assigned to the least accessible site Ⅲ in the centre of a hexagonal prism, A_(3) to site I displaced from a six-ring into the ellipsoidal cage and A_(2) to the most accessible site Ⅳ near an eight-ring window based on adsorption of oxygen and hydrogen and ^(31)P modulations from the SAPO framework observed by ESEM. Oxygen and water oxidize Pd_(I) lons in an activated sample to Pd^(Ⅱ) ions complexed to O_(2)^(-), indicating water decomposition. Adsorption of methanol and ethanol causes a change in the EPR spectrum which indicates some relocation of Pd^(Ⅰ) to allow better coordination with one molecule of the alcohol. Exposure to ethene also changes the EPR spectrum, indicating interaction of Pd^(Ⅰ) with it. ESEM shows that the Pd^(Ⅰ) species coordinates to one ethene molecule. The adsorption of carbon monoxide results in a Pd^(Ⅰ) complex with three molecules of carbon monoxide based on resolved ^(13)C superhyperfine splittings. Upon adsorption of ammonia, one molecule of ammonia coordinates to Pd^(Ⅰ) based on resolved nitrogen hyperfine coupling.

유기 수은 디티존 착물의 분광학적 연구

백건호,박두철 國立昌原大學校 基礎科學硏究所 1989 基礎科學硏究所論文集 Vol.1 No.-

1:1 complex of organomercury(Ⅱ) cation HgR(R=2.6dichloro-4amino phenyl) and dithizon and mercury dithizonate have been prepared, characterized and examined for their photochemical and photochromic behavior is solution and solid state with IR, visible, NMR spectrophotometer. The above two complex are photochromic under steady illumination with visible light. very fast, than 1:2 complex. The photochemical stability of the complex in to luene solution to ultraviolet decrease in the order 1:2 complex > 1:1 complex.

ESR 및 ESEM을 이용한 MnAPSO-34 Mn(Ⅱ)의 골격치환에 대한 분광학적 증거

백건호 昌原大學校 基礎科學硏究所 1998 基礎科學硏究所論文集 Vol.10 No.-

Electron Spin Echo modulation analysis of 0.1 mole of MnAPSO-34 with adsorbed D₂O shows two deuteriums at 0.29 nm and two at 0.30 nm from Mn. At low manganese content (0.05 mole %) in MnH-SAPO-34 with adsorbed D₂O shows four deuteriums at 0.31 nm and two at 0.31 nm from Mn. This suggests that two waters hydrate an MnO₄ configuration with a D-O bond orientation for the waters as expected for a negatively charged site. The framework incorporation in MnAPSO-34 is confirmed by a three-pulse ESEM study of deuterium modulation resulting from interactions of deuterated adsorbates with manganese which indicates that the manganese occupies a negative charged site in MnAPSO-34.

SAPO-34 분자체의 Pd(Ⅰ) 화학 종의 구조 및 반응성에 관한 EPR 및 ESEM 분광학적 연구

백건호,허선도 昌原大學校 基礎科學硏究所 2001 基礎科學硏究所論文集 Vol.13 No.-

SAPO-34를 합성하는 동안에 Pd(NH3)4Cl2를 가하여 생성된 PdH-SAPO-34를 탈수 및 산화 환원과정을 진행하고 여기에 O2 흡착제와의 상호작용을 (S)PdH-SAPO-34와 (i)PdH-SAPO-34을 비교 연구하였다. (S)와 (i)는 각각 고체상 이온교환 반응과 액체상 이온교환 반응을 나타낸다. 전자 상자기 공명(EPR) 및 전자 스핀-이코 분광법(ESEM)은 2개의 다르게 합성한 시료에 대하여 거의 같다. 600℃에서 활성화된 시료에서는 3 개의 다른 Pd(I) 화학 종이 관측되었다. : 공통적인 gⅡ = 2.92를 갖고 3 개의 수직 성분 A1(gㅗ = 2.18) A2(gㅗ = 2.14)와 A3(gㅗ = 2.07) 를 갖으며 외부 골격에 3 개의 양이온 자리가 있음을 의미한다. Oxygen blowing 실험과 인-모듈화 실험을 근거로 A1은 육각 프리즘의 중심 site Ⅲ, A2는 가장 정관하기 쉬운 8 원환 창 가까이에 있는 sixte IV이고 A3는 6원환 창에서 타원형 주머니(ellipsoidal cage)로 이동한 site I로 지정하였다.

CF₂Cl₂를 이용한 탄소 및 염소의 동위원소 분리

白建鎬 國立 昌原大學校 産業技術硏究所 1987 産技硏論文集 Vol.1 No.-

1. 농축인자는 레이저 펄스수에 따라 지수함수적으로 증가하며 펄스당 분해율은 CF2Cl₂/O₂ 계에서는 8.8×10-4 으로 Fettweiss등의 실험치 6.3×10-4보다 높은 값을 나타내었다. 2. 시료(CF2Cl₂)의 압력을 고정시키고 라디칼 스캐벤저(O₂, NO)의 압력을 증가시키므로서 최대농축인자 최적 혼합비(CF2Cl₂/O₂ 계 50/150, CF2Cl₂/NO 계 50/200)를 구하였다. 3. 레이저 조사파장을 변화시켜서 동위원소 농축인자(β13, β37)를 측정하여 최적파장(10.6㎛ P38)을 구하였다. 4. 이와 같이 얻은 최적파장, 최적 혼합비에서 펄스수 2,500에서 최대 농축인자 β13=10, β37=1.6을 각각 얻었다. 5. 광 반응 생성물을 분석하여 CF2Cl₂/O₂ 및 CF2Cl₂/NO계의 광 반응 기구를 제안하였다. The isotope(C13, Cl37) separation in the CF₂Cl₂/O₂ and CF₂Cl₂/O₂ and CF₂Cl₂/NO systems was investigated by employing TEA CO₂ laser in a static cell. The exponential behavior of enrichment factor (β) versus pulse number (N) was found and the dissociation rate per pulse for CF₂Cl₂/O₂ system was 8.8×10-4. The optimum mixing ratios, 50/150 for CF₂Cl₂/O₂ system and 50/200 for CF₂Cl₂/NO system, were obtained by increasing the pressure of radical scavengers (O₂ or NO) at constant pressure of sample CF₂Cl₂). The optimum wave length of 10.6㎛ P38 was obtained by observing C13 isotope enrichment factor at various induced laser wave-lengths. The enrichment factors obtained at the optimum experimental conditions (wave-length, mixing ratio) were β13=10, β37=1.6. The mechanism of the photochemical reactions for the CF₂Cl₂/O₂ and CF₂Cl₂/NO systems were proposed on the basis of the reaction products.

EPR 및 ESEM을 이용한 MoH-SAPO-34의 Mo(V)의 화학종, 위치 및 흡착상호작용에 관한 연구

백건호,김재원 昌原大學校 基礎科學硏究所 1996 基礎科學硏究所論文集 Vol.8 No.-

A solid state reaction of MoO₃with as synthesized SAPO-34 generates paramagnetic Mo(V) species. However, subsequent dehydration results weak Mo(V) species, subsequent activation results in the formation of Mo(V) species which are characterized by ESR. The ESR and ESEM results indicate that the oxomolybdenum species, likely ??, or ?? The ?? species seem more probable because of the following reasons. Since SAPO-34 have a low negative framework charge. more positive charged species, like ??are not as easily stabilized. A rhombic ESR signal is observed after adsorption of D₂O, CD₃OH CH₃CH₂OD and ND₃. Upon O₂adsorption the Mo(V) ESR signal intensity decreases and O₂radical is formed. The location and coordination geometry of Mo(V) has been determined by three-pulse electron spin echo modulation data and simulation. After adsorption of methanol, ethanol, ethene, or ammonia, for MoH-SAPO-34, Mo(V) is directly coordinated only to one molecule, respect, but to two D₂O as same result of MoH-SAPO-5.

4-(p-dimethylaminobenzeneazo)phenylmercuric dithizonate의 합성 및 염료로서의 적합성 연구

백건호,임남수 國立 昌原大學校 基礎科學硏究所 1994 基礎科學硏究所論文集 Vol.6 No.-

1:1 Complex of organomercury cation HgR^(+) (Ⅰ; R= 4-(p-dimethylamino benzeneazo)phenyl, Ⅱ; R=p-N, N-dimethylaminophenyl) and dithizone have been prepared, characterized, and examined for their photochemical and phototropic behavior in solution and thermal stability for their solid state with IR, Visible, NMR spectrophotometer, DSC, TGA. The photochemical stability of 4-(p-dimethylaminobenzeneazo)phenylmercuric dithizonate in n-propyl alcohol and thermal stability for the solid state were better than those of p-N, N-dimethylaminophenylmercuric dithizonate.

EPR 및 ESEM을 이용한 VH-SAPO-34의 V(IV)화학종, 위치 및 흡착상호작용에 관한 연구

백건호 昌原大學校 基礎科學硏究所 1995 基礎科學硏究所論文集 Vol.7 No.-

A solid state reaction of VOSO₄XH₂O and ?? with as-synthesized SAPO-34 generates paramagnetic V(IV) species. However, subsequent oxidation results weak paramagnetic V(IV) species. However, subsequent oxidation results weak paramagnetic V(IV) species, subsequent activation results in the formation of V(IV) species which are characterized by ESR. The ESR and ESEM results indicates that the V(IV) species exist as vanadly ion either as ?? or ??. The ?? species seem more probable because of the following reasons. Since SAPO-34 have a low negative framework ??, more positively charged species, like ?? are not as easily stabilized. Tetravalent vanadium ion can only be observed at or below 77K, the activated sample of VH-SAPO-34 can be measured even at room temperature. After adsorption of methanol, ethanol, propanol or ethene, EPR and ESEM data show that only one molecule coordinates to ?? respectively.

4-(p-dimethylaminobenzeneazo)phenymercuric dithizonate의 합성 및 염료로서의 적합성 연구

백건호,임남수 國立昌原大學校 基礎科學硏究所 1994 基礎科學硏究所論文集 Vol.6 No.-

1:1 Complex of organomercury cation HgR?(Ⅰ; R= 4-(p-dimethylamino benzeneazo) phenyl, Ⅱ; R=p-N, N-dimethylaminophenyl) and dithizone have been prepared, characterized, and examined for their photochemical and phototropic behavior in solution and thermal stability for their solid with IR, Visible, NMR spectrophotometer, DSC, TGA. The photochemical stability of 4-(p-dimethylaminobenzeneazo)phenylmercuric dithizonate in n-propyl alcohol and thermal stability for the solid state were better than those of p-N, N-dimethylaminophenylmercuric dithizonate.

폴리에스터 섬유에 응용되는 Photochromic 분산염료에 있는 치환기효과에 따른 염착량의 변화

이은정,백건호 國立 昌原大學校 基礎科學硏究所 1993 基礎科學硏究所論文集 Vol.4 No.-

1:1 Complex of (Ⅰ;R=4-amino-2,6-dichlorophenyl,Ⅱ;R=4-amino-3,5-dichlorophenyl) organomercury cation ?? and dithizone have been synthesized. Indication of hydrogen bond of these compounds with polyester was obtained from solvent extraction studies. The return time ofⅠdispersion dye dissolved in toluene from orange through blue to original colour was 22.5 minutes and was 12 minutes in case of sample Ⅱ. Thermal stability of Ⅰ was higher than that of Ⅱ by +Ⅰ effect of electron releasing group but photochemical stability of Ⅰ solution dissolved in toluene was similar to that of Ⅱ dispersion dye solution. Optimal pH of Ⅰ & Ⅱ was 6, and 7, respectively. Amount taken up by Ⅰ was 14 times higher than by Ⅱ.