理論計算對於小分子在觸媒上產氫之研究

行政院國家科學委員會專題研究計畫 成果報告

理論計算對於小分子在觸媒上產氫之研究(第 3 年) 研究成果報告(完整版)

計 畫 類 別 ： 個別型

計 畫 編 號 ： NSC 98-2113-M-011-001-MY3

執 行 期 間 ： 100 年 08 月 01 日至 101 年 07 月 31 日 執 行 單 位 ： 國立臺灣科技大學化學工程系

計 畫 主 持 人 ： 江志強

報 告 附 件 ： 出席國際會議研究心得報告及發表論文

公 開 資 訊 ： 本計畫可公開查詢

中 華 民 國 101 年 10 月 29 日

中 文 摘 要 ： 三年的研究計畫，將使用 slab 及 cluster 兩種模式結合泛 函密度理論之計算，來研究小分子在觸媒上產生氫氣或脫氫 之反應機制。藉由理論計算可提供 XRD、STM、XPS、UPS 等資 訊與實驗結果作比較，以鑑定表面性質；DOS 及 electron density difference 的分析，用以了解小分子與觸媒表面的 作用力；反應位能、反應物、過渡態及產物之能量相關資 訊，得以窺見小分子在觸媒表面的反應機制。本研究計畫三 年內將完成以下目標：

(1) H2O dehydrogenation over Pt, Ru, Ir, Pd, Cu , Ni, ZnO, RuO2, RuSe2 and IrO2 surfaces.

(2) NH3 dehydrogenation over Ru, Ir, Pt, RuO2, RuSe2 and IrO2 surfaces.

(3) CH4 dehydrogenation over Ru, Ir, Pt, Pd and Ni surfaces.

(4) HCOOH decomposition over RuO2, RuSe2 and IrO2 surfaces.

(5) CH4 steam reforming over Cu or Ni/Al2O3, Cu or Ni/ZnO surfaces.

中文關鍵詞： 銅、鎳、氧化鋅、氧化釕、氧化銥及硒化釕

英 文 摘 要 ： A three-year project is proposed to study the mechanism for hydrogen production from small molecules, such as H2O, NH3 and CH4, over the

catalysts. We will use both periodic slab and cluster model combined with DFT calculations to explore the possible reaction pathways. The analysis, based on DFT calculations, will provide detailed information of XRD, STM, XPS and UPS to compare with the

available experimental results for the

characterization of surfaces； density of states (DOS) and electron density difference contour maps to characterize the nature of molecules adsorption on catalyst surfaces； and the energetics of the

potential minima, transition states, and the reaction potential surfaces to shed light on the reaction mechanism. The work items in three years include:

(1) H2O dehydrogenation over Pt, Ru, Ir, Pd, Cu , Ni, ZnO, RuO2, RuSe2 and IrO2 surfaces.

(2) NH3 dehydrogenation over Ru, Ir, Pt, RuO2, RuSe2

and IrO2 surfaces.

(3) CH4 dehydrogenation over Ru, Ir, Pt, Pd and Ni surfaces.

(4) HCOOH decomposition over RuO2, RuSe2 and IrO2 surfaces.

(5) CH4 steam reforming over Cu or Ni/Al2O3, Cu or Ni/ZnO surfaces.

英文關鍵詞： Cu , Ni, ZnO, RuO2,RuSe2 and IrO2

行政院國家科學委員會補助專題研究計畫

^{■成果報告}

□期中進度報告

理論計算對於小分子在觸媒上產氫之研究

計畫類別：■個別型計畫 □整合型計畫 計畫編號：NSC 98－2113－M－011－001－MY3 執行期間： 98 年 8 月 1 日至 101 年 7 月 31 日

執行機構及系所：台灣科技大學化工系

計畫主持人：江志強 共同主持人：

計畫參與人員：王嘉慶、陶凡、姜欣妮、武成功、王成祐、范桐、羅立偉、吳 軍毅、李秉諺、呂尚霖、賴冠華、陳祈良、王暉棠、曾杰玉、賴柏融

成果報告類型(依經費核定清單規定繳交)：□精簡報告 ■完整報告

本計畫除繳交成果報告外，另須繳交以下出國心得報告：

□赴國外出差或研習心得報告

□赴大陸地區出差或研習心得報告

■出席國際學術會議心得報告

□國際合作研究計畫國外研究報告

處理方式：除列管計畫及下列情形者外，得立即公開查詢

□涉及專利或其他智慧財產權，□一年■二年後可公開查詢

中 華 民 國 101 年 10 月 29 日

中文摘要

關鍵詞：銅、鎳、氧化鋅、氧化釕、氧化銥及硒化釕

三年的研究計畫，將使用slab 及cluster 兩種模式結合泛函密度理論之計算，來 研究小分子在觸媒上產生氫氣或脫氫之反應機制。藉由理論計算可提供XRD、

STM、XPS、UPS等資訊與實驗結果作比較，以鑑定表面性質；DOS 及electron density difference 的分析，用以了解小分子與觸媒表面的作用力；反應位能、反 應物、過渡態及產物之能量相關資訊，得以窺見小分子在觸媒表面的反應機制。

本研究計畫三年內將完成以下目標：

(1) H

2

O dehydrogenation over Pt, Ru, Ir, Pd, Cu , Ni, ZnO, RuO

2,

RuSe

2

and IrO

2

surfaces.

(2) NH

3

dehydrogenation over Ru, Ir, Pt, RuO

2,

RuSe

2

and IrO

2

surfaces.

(3) CH

4

dehydrogenation over Ru, Ir, Pt, Pd and Ni surfaces.

(4) HCOOH decomposition over RuO

2,

RuSe

2

and IrO

2

surfaces.

(5) CH

4

steam reforming over Cu or Ni/Al

2

O

3

, Cu or Ni/ZnO surfaces.

英文摘要

Keywords: Cu , Ni, ZnO, RuO

2,

RuSe

2

and IrO

2

A three-year project is proposed to study the mechanism for hydrogen production from small molecules, such as H

2

O, NH

3

and CH

4

, over the catalysts. We will use both periodic slab and cluster model combined with DFT calculations to explore the possible reaction pathways. The analysis, based on DFT calculations, will provide detailed information of XRD, STM, XPS and UPS to compare with the available experimental results for the characterization of surfaces; density of states (DOS) and electron density difference contour maps to characterize the nature of molecules adsorption on catalyst surfaces; and the energetics of the potential minima, transition states, and the reaction potential surfaces to shed light on the reaction mechanism.

The work items in three years include:

(1) H

2

O dehydrogenation over Pt, Ru, Ir, Pd, Cu , Ni, ZnO, RuO

2,

RuSe

2

and IrO

2

surfaces.

(2) NH

3

dehydrogenation over Ru, Ir, Pt, RuO

2,

RuSe

2

and IrO

2

surfaces.

(3) CH

4

dehydrogenation over Ru, Ir, Pt, Pd and Ni surfaces.

(4) HCOOH decomposition over RuO

2,

RuSe

2

and IrO

2

surfaces.

(5) CH

4

steam reforming over Cu or Ni/Al

2

O

3

, Cu or Ni/ZnO surfaces.

Background of the proposed study

Energy is necessary for all activity. Nowadays, most of the present world energy demand comes from fossil fuel which may eventually run out anyway and had caused major pollution problems such as greenhouse gas emissions. Therefore, finding renewable alternatives is an urgent subject. Fortunately, hydrogen fuel cells offer a unique combination of efficiency and ultra-low emissions, such as PEMFCs, SOFCs and MCFCs use hydrogen as a fuel and produce zero pollution; the byproducts are just water and heat. As a result, the prospect of hydrogen becoming the main fuel for all energy-related a ppl i c at i ons , a “ hydr oge n ec onomy, ” a nd t he c ont i nui ng

development of fuel cells to utilize hydrogen fuel has generated growing interest.

Several sources for hydrogen are now considered: Methanol, ethanol, ammonia, gasoline, water and natural gas are the possible candidates for an efficient production of hydrogen.[1] On the other hand, methanol steam reforming has been thoroughly studied in recent years. Methanol, which is mainly prepared by syn-gas conversion, has a favorable H: C ratio of 4, is available as an abundant feedstock and already largely distributed. Nevertheless, the main drawback of methanol, beside its relatively high toxicity, is that its production is essentially based on reforming of nonrenewable fossil fuels, and therefore its use as a feedstock for electrical vehicle will release fossil carbon into the atmosphere. [2] Ethanol appears as an attractive alternative to

methanol due to economic and environmental reasons.[2-4] Experimental studies about ethanol steam reforming have been published extensively, and several catalysts have been proposed which show sufficient activity and stability to be further

considered or practical applications [5-12]. Thermodynamic studies also have shown the feasibility of hydrogen production from this reaction [13, 14]. Ethanol

decomposition to hydrogen includes two routes: dehydrogenation and dehydration.

Dehydrogenation reaction produces acetaldehyde as intermediate product which can further undergo decomposition leads to methane and carbon monoxide. On the other hand, ethanol dehydration reaction leads to ethylene production which is an

undesirable pathway. Because ethylene is known as coke precursor and carbon

formation is primarily attributed to its presence in the product stream. The role of

catalyst plays an important role on the conversion efficiency and selectivity of such

reaction. Since ethanol includes O-H, C-H, C-C and C-O bonds, the reaction

pathways of ethanol steam reforming over different catalysts are very complicated

and still unknown. As the best knowledge we know, there are still no suitable catalyst

which with both good conversion efficiency and selectivity for such reaction. The

main problem found when using these catalysts is deactivation by sintering and coke

formation. So far, the development of catalyst for ethanol reforming is basically

a trial-and-error approach. In order to unveil the reaction mechanism of ethanol reforming on catalyst, we would start in the investigation of the H

2

production from small and simple molecules on catalysts. Water is the most abundant compound in the biosphere and covers most real solid surfaces. The interaction of water with solid surfaces plays an important role in a variety of phenomena in nature.[15, 16] The understanding of the water-surface interaction is essential to design, optimize, and control such processes. Recently, the interaction of water monomers, dimers, and hexamers with Ag(111), Cu(111), Pd(111), Ru(0001), and Pt(111) surfaces were studied by scanning tunneling microscopy (STM). [17-21] Density functional theory (DFT) calculations were applied to study water adsorption on Cu(111), Cu(110), Pt(111), Rh(111), Pd(111), Au(111), and Ru(0001) surfaces.[22-24] As a clean and recyclable energy source, hydrogen production by overall water splitting under solar radiation using a heterogeneous photocatalyst has attracted substantial interest in recent years as a potentially useful means of solar energy conversion.

Thermodynamically, the overall water splitting reaction is an uphill reaction with a large positive change in Gibbs free energy (+238 kJ/mol). There is an activation barrier in the charge-transfer process between photocatalysts and water molecules, necessitating a photon energy greater than the band gap of the photocatalyst to drive the overall water splitting reaction at reasonable reaction rates. In addition, the

backward reaction, that is, water formation from H

2

and O

2

, must be strictly inhibited, and the photocatalysts themselves must be stable in the reaction. Furthermore,

although there are a large number of materials that possess suitable band gap potentials, there are very few materials that function as a photocatalyst for overall water splitting due to other factors, as mentioned below. As shown in Figure 1, the overall water splitting reaction on a semiconductor photocatalyst occurs in three steps.

The first two steps are strongly dependent on the structural and electronic properties of the photocatalyst. In general, high crystallinity has a positive effect on activity since the density of defects, which act as recombination centers between

photogenerated carriers, decreases with increasing crystallinity. The third step is

promoted by the presence of a solid cocatalyst.

Figure 1. Processes involved in photocatalytic overall water splitting on a heterogeneous photocatalyst.[25]

The cocatalyst is typically a noble metal (e.g., Pt, Rh) or metal oxide (e.g., NiO, RuO

2

) and is loaded onto the photocatalyst surface as a dispersion of nanoparticles to produce active sites and reduce the activation energy for gas evolution.[25-32] It is thus important to design both the bulk and surface properties of the material carefully so as to obtain high photocatalytic activity for this reaction. In this proposal, we only focus on the study the H

2

O molecule reaction on cocatalyst.

The decomposition of ammonia (NH

3

) is an important industrial reaction. The catalytic oxidation of NH

3

to NO, the so-called Ostwald process, is a key step in the production of nitric acid. In addition, the oxidation of NH

3

leading to N

2

and H

2

O has become of increasing interest in connection with the removal of NH

3

from waste streams.[33] Another potentially important application of NH

3

is its use as a hydrogen source and storage substance for fuel cells.[34– 36] Because of these and other

technological, economical, and environmental factors, a large number of reports have described the decomposition and oxidation reactions of NH

3

.[37– 40] The most critical factor in determining the reactivity and selectivity of these reactions is the nature of the catalyst. Several materials have been investigated as catalysts for NH

3

dissociation reactions, including metals,[5,6] alloys,[7] and metal oxides.[40,41] Our recent work [42] assessed the adsorption and relative stability of ammonia and the resulting dehydrogenated NH

x

species (x = 0, 1, 2) on RuO

2

(110) surfaces using periodic slab DFT calculations. In addition, our primary results indicate H

2

production from NH

3

dehydrogenation on metal oxides is practical. Therefore, NH

3

molecule may be the good candidate as the H

2

source.

The study of the dynamics of dissociative adsorption of CH

4

on transition metal

surfaces has a history several decades long and is still of great current interest. In part this is related to the rate-limiting role of CH

4

dissociative adsorption in important industrial catalytic processes, e.g., steam reforming. It is hoped that a detailed understanding of the dissociative adsorption may one day lead to some optimization of the processes, although at present little practical guidance has arisen from such studies. Another major motivation for interest in this dynamics is that CH

4

dissociation at metal surfaces generally requires activation, i.e., there is a barrier to dissociation, so that this system becomes an important prototype for developing fundamental understanding of the dynamics of activated adsorption. The dissociative adsorption of CH

4

has previously been investigated on several transition metal

surfaces via molecular beam techniques.[43– 51] The activated dissociative adsorption observed on all surfaces, a few transition metal surfaces also exhibit low E channels of dissociation as well. For example, precursor-mediated processes are proposed for CH

4

dissociation on Ir(110)[48, 52] and Ir(111).[49] Also, a nonactivated steering mechanism has been proposed for CH

4

dissociation on Pt(110).[51] As a method of converting the natural gas to hydrogen must be performed by reforming reactions using H

2

O or CO

2

, and the partial oxidation reaction.

Steam and CO2reforming of methane are large endothermic reactions. Therefore, in these conventional processes, significant problems are involved in economically producing large amounts of hydrogen.In addition,fuelcell’shydrogen production without CO is required,

because CO poisons the electrode. CO is also produced through steam reforming, CO2

reforming and partial oxidation of methane. CO should be converted to CO2through the water gas shift reaction

in order to obtain pure hydrogen.

If hydrogen could be produced efficiently, it could constitute a clean universal fuel [53]. In hydrogen

production from methane, the decomposition of methane is an effective hydrogen production process. The decomposition of methane has attracted much attention, because the process involves small-side reaction control and reduced CO

2

emissions.

The decomposition of methane can produce hydrogen only as a gaseous product [54–

56]. It has been reported that steam contact with nickel, results very often in formation

of OH groups

[57]. Thus, under hydrocarbon steam reforming reaction conditions, Ni

catalyst surface may have an important coverage of OH radicals and O atoms, instead of water molecules. Moreover, the investigation of steam adsorption mechanism on various supported Ni-based catalyst, has shown that magnesia support is active for steam dissociation and that its spillover probably involves OH species instead of molecular water

[58].During high temperature methane steam reforming reactions, the

CH

x

surface species could react with adsorbed oxygen to give carbon monoxide

[59].

On the other hand, for low temperature MSR test carried out on Ni/Al

2

O

3

catalyst, it

has been suggested that OH groups have an important mechanistic participation in

carbon dioxide production

[60]. Also, from a kinetic model developed for Ni/MgO

and Ni/TiO

2

it has been concluded that CH

x

intermediates absorbed on nickel react with surface OH groups

[61].

Results

In this study, we have completed the calculations of

1. NH

3

adsorption and oxidation on RuO

2

and IrO

2

(110) surfaces 2. CH

4

adsorption and decomposition on IrO

2

(110) surface

3. Ethanol decomposition on α-Al

2

O

3

and Ni/α- Al

2

O

3

surfaces 4. WGS on Cu/α- Al

2

O

3

, Pd/ZnO and Cu/ZnO surfaces

5. Methanol adsorption and decomposition on ZnO, Pd/ZnO and Cu/ZnO surfaces Parts of the results have published to

Langmuir 2010, 26, 15845.

J. Phys. Chem. C 2010, 114, 18588.

J. Phys. Chem. C 2011, 115, 516.

J. Phys. Chem. C 2011, 115, 19203.

Langmuir 2011, 27, 14253.

J. Phys. Chem. C 2012, 116, 6367.

and parts of results have been submitted to publish or in preparation. In addition, we also developed other researches related to optoelectronic materials. The list of recent three years publications and some of contents are as follows:

SCI publications (2010~2012)

1. Chung, Wen-Hung; Wang, Chia-Ching; Tsai, Dah-Shyang*; Jiang, Jyh-Chiang;

Cheng, Yu-Chang; Fan, Liang-Jen; Yang, Yaw-Wen; Huang,

Ying-Sh e ng, ” Ana l ys i s of De oxyge na t i on on I r O

2

(110): Core-Level Spectroscopy a nd De ns i t y Func t i ona l The or y Ca l c ul a t i on”Surf. Sci. 604 (2010) 118.

2. Tsung-Fan Teng, Wei-Lin Lee, Yi-Fu Chang, Jyh-Chiang Jiang, Jeng-Han Wang*, Wei-Hsiu Hung*, “ Adsorption and Thermal Reactions of H2O and H2S on Ge(100)” 2010, 114, 1019.

3. Norman Lu*, Wen-Han Tu , Yuh-Sheng Wen, Ling-Kang Liu, Chun-Yi Chou and Jyh-Chiang Jiang, “ The Intramolecular Blue-shifting C-H···F-C Hydrogen Bond in Solid State“ , CrystEngComm. 2010, 12, 538.

4. Hsin-Ni Chiang, Ya-Chin Cheng and Jyh-Chiang Jiang*, “ DFT Study of Ethanol Decomposition on Ni/α -Al

2

O

3

(0001) Surface” , Langmuir 2010, 26, 15845.

5. Han-Yu Wu, Kun-Li Wang, Jyh-Chiang Jiang, Der-Jang Liaw*, Kueir-Rarn Lee,

Juin-Yih Lai and Ci-Liang Chen “ Experimental and theoretical investigation of a

new rapid switching near-i nf r a r e d e l ec t r oc hr omi c c onj uga t e d pol yme r ” Journal

of Polymer Science Part A: Polymer Chemistry, 2010, 48, 3913.

6. Chang, C. H., K. L. Wang, J. C. Jiang, D. J. Liaw*, K. R. Lee, J. Y. Lai and K.

H. La i , 2010, “ Nove l Ra pi d Swi t c hi ng a nd Bl e a chi ng El e ctrochromic Polyimides Containing Triarylamine with 2-Phenyl-2-i s opr opyl Gr oups ” , Pol ymer , 2010, 51, 4493.

7. Chen, W. H., K. L. Wang, W. Y. Hung, J. C. Jiang, D. J. Liaw*, K. R. Lee, J. Y.

La i a nd C. L. Che n, 2010, “ Nove l Tr i ar yl a mi ne -Based Alternating Conjugated Polymer with High Hole Mobility: Synthesis, Electro-optical and Electronic Pr ope r t i e s ” , J . Pol ym. Sci . , Pa r t A: Pol ym. Che m. , 2010, 48, 4654.

8. Chia-Ching Wang, Shih Syong Siao and Jyh-Chiang Jiang*, “ DFT Study of NHx (x = 0– 3) and N

2

Adsorption on IrO

2

( 110) Sur f a ce s ” , J. Phys. Chem. C 2010, 114, 18588.

9.

Cheng-Hung Chang, Kun-Li Wang, Jyh-Chiang Jiang, Der-Jang Liaw,*

Kueir-Rarn Lee, Juin-Yih Lai, Kuo Yuan Chiu, Vuhlong Oliver Su, “Synthesis and Computational Oxidation Mechanism Study of Novel Organosoluble

Aramids with High Modulus by Low-TemperatureSolution Polycondensation”

Journal of Polymer Science: Part A: Polymer Chemistry, 2010, 48, 5659.

10. Po-Tuan Chen, Chia-Ching Wang, Jyh-Chiang Jiang*, Hsi-Kai Wang, and Michitoshi Hayashi, “

Barrierless Proton Transfer Within Short Protonated

Peptidesin thePresenceofWaterBridges.A Density FunctionalTheory Study”,

J. Phys. Chem. B 2011, 115, 1485.

11. Jyh-Chaing Jiang, Kuan-Hung Lin, Sz-Chi Li, Pao-Ming Shih, Kai-Chan Hung, S.H. Lin, and Hai-Chou Chang*, “ As s oc i a t i on St r uc t ur e s of I oni c Li qui d/ DMSO Mixtures Studied by High-Pr e s s ur e I nf r a r e d Spe c t r os c opy” , J. Chem. Phys. 2011, 134, 044506.

12. Li-Wei Chou, Ya-Rong Lee , Jyh-Chiang Jiang*, Jiing-Chyuan Lin

^*

, and Juen-Kai Wang*, “ Unraveling molecular adsorption with surface Raman spectroscopy: trans-stilbene, trans,trans-distyrylbenzene and trans-azobenzene on Ag/Ge(111)” , 2011, J. Phys. Chem. C 115, 516.

13. Kun-Li Wang

^*

, Man-kit Leung,

^*

Li-Ga Hsieh, Chin-Chuan Chang, Kueir-Rarn Lee,Chun-Lung Wu, Jyh-Chiang Jiang, Chieh-Yu Tseng, Hui-Tang Wang,

“ Conjugated Polymers Containing Electron-Deficient Main Chains and Electron-rich Pendant Groups: Synthesis and Application to

El e c t r ol umi ne s c e nc e ” , Organic Electronics 12 (2011) 1048.

14. Jyh-Chiang Jiang, Sz-Chi Li, Pao-Ming Shih, Tzu-Chieh Hung, Shu-Chieh

Chang, Sheng Hsien Lin, Hai-Chou Chang,* “ A Hi gh-Pressure Infrared

Spectroscopic Study on the Interaction of Ionic Liquids with PEO-PPO-PEO

Block Copolymers and 1,4-Di oxa ne ” , J. Phys. Chem. B 2011, 115, 883.

15. Wei-Ren Lian, Kun-Li Wang, Jyh-Chiang Jiang, Der-Jang Liaw,* Kueir-Rarn Lee and Juin-Yi h La i , “Ne ut r a l l y c ol our l e s s , t r a ns pa r e nt a nd t her ma l l y s t abl e polynorbornenes via ring-opening metathesis polymerisation for near-infrared e l e c t r oac t i ve a ppl i ca t i ons ” , J . Ma t e r . Che m. 2011,21, 8597–8604.

16. Chang, Hai-Chou ; Hung, Tzu-Chieh; Chang, Shu-Chieh; Jiang, Jyh-Chiang;

Li n, She ng Hs i e n, ”Interactions of Silica Nanoparticles and Ionic Liquids Probed by High Pressure Vibrational Spectroscopy", J. Phys. Chem. C 2011, 115 (24), 11962– 11967.

17.

Wei-Ren Lian, Kun-Li Wang, Jyh-Chiang Jiang, Der-Jang Liaw,* Kueir-Rarn Lee, Juin-Yih Lai, “Preparation ofNeutrally Colorless,Transparent

Polynorbornenes with Multiple Redox-active Chromophores Via Ring-Opening Metathesis Polymerization toward Electrochromic Applications”,

Journal of Polymer Science: Part A: Polymer Chemistry, 2011, 49(15), 3248-3259.

18. Teng, Tsung-Fan; Chou, Chun-Yi; Hung, Wei-Hsiu*; Jiang, Jyh-Chiang*,

“ Appl i c a t i on of De ns i t y Func t i ona l The or y a nd Phot oe l e c t r on Spe c t r a t o t he Adsorption and Reaction of H

2

S on Si ( 100) ” , J. Phys. Chem. C 2011, 115(39), 19203-19209.

19. Wang, Chia-Ching; Siao, Shih Syong; Jiang, Jyh-Chiang,* “ Density Functional Theory Study of the Oxidation of Ammonia on the IrO

2

( 110) Sur f a ce ” , Langmuir 2011, 27, 14253-14259.

20. Hai-Chou Chang,* Shu-Chieh Chang, Tzu-Chieh Hung, Jyh-Chiang Jiang, Jer-La i Kuo, She ng Hs i en Li n, “ A High-Pressure Study of the Effects of TiO

2

Na nopa r t i c l e s on t he St r uc t ur a l Or ga ni za t i on of I oni c Li qui ds ” , J. Phys. Chem. C 2011, 115, 23778-23783.

21. Yu-Chi Pan, Hui-Hsu Gavin Tsai, Jyh-Chiang Jiang, Chia-Chun Kao,

Tsai-Lung Sung, Po-Jui Chiu, Diganta Saikia, Jen-Hsuan Chang and Hsien-Ming Ka o*, “ Probing the Nature and Local Structure of Phosphonic Acid Groups Functionalized in Mesoporous Silica SBA-15 “ , J. Phys. Chem. C 2012, 116, 1658-1669.

22. Wang, Chia-Ching; Siao, Shih Syong; Jiang, Jyh-Chiang,* "C– H Bond Ac t i va t i on of Me t ha ne vi a σ–d Interaction on the IrO

2

(110) Surface: Density Functional Theory Study" J. Phys. Chem. C 2012, 116, 6367.

23. Ermias Girma Leggesse and Jyh-Chiang Jiang*, “ Theoretical Study of the Reductive Decomposition of 1, 3-Propane Sultone: SEI Forming Additive in Lithium-ion battery” , RSC Advances 2012, 2, 5439.

24. Ermias Girma Leggesse and Jyh-Chiang Jiang*, “ Theoretical Study of the

Reductive Decomposition of Ethylene Sulfite: SEI Forming Additive in

Lithium-i on ba t t e r y” , J. Phys. Chem. A (in press)

25. Huei-Tang Wang, Fadlilatul Taufany, and Jyh-Chiang Jiang*, “ DFT-TDDFT Molecular Design of Ruthenium Dye-Sensitizers with Improved Metal-to-Ligand Charge Transfer Contributions” , (submit to Langmuir)

26. Ermias Girma Leggesse, Rao Tung Lin, Jyh-Chiang Jiang*, “ Theoretical Investigation of the Oxidative Decomposition of Propylene Carbonate and Vinylene Carbonate Based Electrolytes in Lithium ion Batteries” , (submit to J.

Power Sources)

27. Atetegeb Meazah Haregewoin, Ermias Girma Leggesse, Jyh-Chiang Jiang*, Fu-Ming Wang, Bing-Joe Hwang, Shawn D Lin*, “ A Combined Experimental and Theoretical Study for Understanding of Surface Film Formation: Effect of Oxygen on Reduction Mechanism of Propylene Carbonate” , (submit to J. Power Sources)

28. “ Theoretical investigations of metal-free dyes for solar cells: Effects of electron donor a nd a cc e pt or gr oups on s e ns i t i ze r s ” , Nachimuthu Santhanamoorthi, Kuan-Hwa Lai, FadlilatulTaufany and Jyh-Chiang Jiang*, (submit to RSC Advances)

29. Wang, Chia-Ching; Wu, Jyun-Yi; Jiang, Jyh-Chiang*, "Microkinetic Simulation of Temperature Programmed Desorption", (submit to JPCC) 30. Hsin-Ni Chiang; J.C. Jiang*, “ De ns i t y Func t i ona lTheory Study of

Water-Gas-Shift Reaction on 3Cu/Al

2

O

3

( 0001) Sur f a ce ” , ( s ubmi t to J. Catal.) 31. Vo Thanh Cong, Lam K. Huynh, J-Y. Hung and Jyh-Chaing Jiang*, “ Me t ha nol

Adsorption and Decomposition on ZnO

(1 01 0 )

Surface: A Density Functional The or y St udy”,(submit to J. Chem. Phys.)

32. Cong T. Vo, Lam K. Huynh, and Jyh-Chaing Jiang*, “ CO Adsorption and Oxidation on Undoped and Ti-doped ZnO

(1 0 1 0 )

Surfaces: A Density Function The or y St udy”,(submit to J. Phys. Chem. C)

研討會報告(Invited talk)

1. “ Computational Chemistry in Heterogeneous Catalysis: from Elucidation to Prediction” , PCCP, Taipei, 2012/9/19~2012/91/21, 1

^st

International Conference on Material Chemistry: Theoretical, Computational and Experimental

Perspectives.

2. “ The or e t i cal Study of Ammonia Oxidation on RuO

2

(110) Surfaces: Mechanism a nd Mi c r oki ne t i c s ” , 西安，2012, 8/7~10，第五屆海峽兩岸理論化學研討會.

3. “ Ammoni a Oxi da t i on on RuO

2

(1 1 0) Surface: DFT Calculations Combined with Mi c r oki ne t i c Ana l ys i s ” , HCMcity, Vietnam, 2011/12/20, 1

^st

International

Conference on Computational Science and Engineering

4. “ Computational Chemistry in Catalysis” , NTU, 2011/10/21, Catalysis Workshop

on Operando Spectroscopy.

5. “ TheRole of Computational Chemistry in Experiments: from Elucidation to Prediction ", Surabaya, Indonesia, 2011/10/13, ICOMSc.

6. “ Theoretical and Computational Chemistry in Catalytic Reaction” , 金門，

2011/1/13，第四屆海峽兩岸理論化學研討會.

7. “ Catalytic Activity of IrO

2

( 110) s ur f ac e : A DFT s t udy” , Taipei, 2010/10/8, 13

^th

Asia-Pacific Journal of Chemical Engineering (APCChE 2010).

8. “ Catalytic Activity of IrO

2

( 110) s ur f ac e : A DFT s t udy” , Japan, 2010/6/24, 13

^th

International Conference on Theoretical Aspects of Catalysis (ICTAC-13).

研討會論文

1. “

DFT-TDDFT Molecular Design of Ruthenium Dye-Sensitizers with Improved Metal-to-Ligand Charge Transfer Contributions”

, Huei-Tang Wang, Fadlilatul Taufany, and Jyh-Chiang Jiang,

^

(oral presentation), 28-30 December 2011, HKUST, Hong Kong. The Advanced Electrochemical Energy Symposium.

2. “Th

eoreticalstudiesoftheReductiveDecomposition of Ethylene sulfite: SEI Forming Additive in Lithium-ion battery”(oral presentation), Ermias Girma

Leggesse and Jyh-Chiang Jiang*, 28-30 December 2011, HKUST, Hong Kong.

The Advanced Electrochemical Energy Symposium.

3. “

Theoretical Study of Electro-optical Properties in D-A Conjugated Oligomers”

(oral presentation), Chieh-Yu Tseng, Kuan-Hwa Lai ,Chi-Liang Chen and Jyh-Chiang Jiang*, 28-30 December 2011, HKUST, Hong Kong. The Advanced Electrochemical Energy Symposium.

4. “Density Functional Theory Study of Water Gas Shift Reaction on Cu/ZnO

(1 0 1 0 ) Surface”

, Cong Thanh Vo, Lam Kim Huynh, and Jyh-Chiang Jiang*

(oral presentation), Dec. 19-21

^st

, 2011, HCMC, Vietnam, The First International Conference on Computational Science and Technology(1

^st

ICCSE).

5. “ Comparison of CO oxidation on undoped ZnO and Ti-doped ZnO Surfaces: A DFT Study” , Cong Thanh Vo, Lam Kim Huynh, J-Y. Hung, and Jyh-Chiang Jiang* (poster), Dec. 19-21

^st

, 2011, HCMC, Vietnam, The First International Conference on Computational Science and Technology (1

^st

ICCSE).

6. “ Theoretical Investigation of the Oxidative Decomposition of Propylene

Ca r bona t e a nd Vi nyl e ne Ca r bona t e Ba s e d El e c t r ol yt e s i n Li t hi um i on Ba t t er i e s ” , Ermias Girma Leggesse, Jyh-Chiang Jiang, June 17th to 22nd, 2012 in Jeju, 16th International Meeting on Lithium Batteries (IMLB 2012).

7. “ Microkinetic Modeling of Ammonia Oxidation on RuO

2

(110) Surfaces” ,

Chia-Ching Wang, Jyun-Yi Wu and Jyh-Chiang Jiang, June 26 to 30 2012, in

Vlissingen, The Netherlands, 14

^th

International Conference on Theoretical Aspects

of Catalysis (ICTAC-14)

國科會補助專題研究計畫項下出席國際學術會議心 得報告

日期：100 年 11 月 5 日

此會議為印尼 ITS 大學理學院所主辦，參與領域包含數學、物理及化學相關理論 計算領域。個人則受邀擔任 Keynote Speaker，因此演講的題目較大，主要著重 於計算化學對於實驗方面所扮演角色，就個人經驗敘述從詮釋實驗結果只設計與 預測實驗。由於印尼 ITS 大學有意願發展理論計算化學，會後我亦到化學系給與 另一場演講，主要介紹利用理論計算設計新材料。印尼學術環境相當落後，當地 教授授課負擔重，研究不易，但當地政府似乎有改革的決心，教育預算 2011 年 倍增，加上印尼有豐富的資源，其進步可以預期。

日期：101 年 1 月 5 日 計畫編

號

NSC 98－2113－M－011－001－MY3

計畫名 稱

理論計算對於小分子在觸媒上產氫之研究

出國人

員姓名 江志強 服務機構

及職稱

台科大化工系 教授

會議時 間

100 年 10 月 12 日 至

100 年 10 月 13 日

會議地點

印尼-泗水

會議名 稱

(中文)關於數學及科學的國際研討會

(英文) International Conference on Mathematics and Science (ICOMSc)

發表論 文題目

The Role of Computational Chemistry in Experiments: from Elucidation to Prediction

計畫編 號

NSC 98－2113－M－011－001－MY3

計畫名 稱

理論計算對於小分子在觸媒上產氫之研究

出國人

員姓名 江志強 服務機構

及職稱

台科大化工系 教授

會議時 間

100 年 12 月 19 日 至

100 年 12 月 21 日

會議地點

越南-胡志明市

此會議由胡志明市科技大學新成立的計算科學與工程學院所舉辦，主要根據過去 台越雙邊計算化學研討會擴充成國際研討會，國內參與者有林明彰院士、原分所 周美吟所長及郭哲來博士。個人首次拜訪胡志明市，並受邀為 invited speaker，

主要介紹這幾年我們催化反應研究的進展，另外我一個越南籍的博士班研究生亦 參與此會議，並給予口頭報告與壁報論文。越南雖是一個共產且落後國家，但其 政府很注重理論計算這領域，因此成立計算科學與工程學院，可以整合並發展完 整的理論計算科學，而台灣在此領域發展雖早，但各自為政，未有前瞻的發展計 畫。

日期：101 年 7 月 25 日

ICTAC 為兩年一次的研討會，兩年前個人亦受邀在 ICTAC-13 擔任 invited speaker。

相較於其他研討會，此會議與我們的研究最有關係，此次僅以壁報論文發表。參 與此會，看到國際知名學者敘述各種理論計算領域應用在催化反應的發展，如：

J. Sauer (Towards Predictions of Energies and Free Energies for Molecule-Surface Interactions with Chemical Accuracy), J. Hafner (Challenges in Catalysis research based on density functional theory: Complexity, dynamics, correlation), D. G.

Vlachos (Recent advances in multiscale modeling: Application to biomass 會議名

稱

(中文)首屆計算科學與工程國際研討會

(英文) 1

^st

International Conference on Computational Science and Engineering

發表論 文題目

Ammonia Oxidation on RuO

2

(1 1 0) Surface: DFT Calculations Combined with Microkinetic Analysis

計畫編 號

NSC 98－2113－M－011－001－MY3

計畫名 稱

理論計算對於小分子在觸媒上產氫之研究

出國人

員姓名 江志強 服務機構

及職稱

台科大化工系 教授

會議時 間

101 年 6 月 26 日 至

101 年 6 月 30 日

會議地點

荷蘭-Vlissingen

會議名 稱

(中文)第十四屆關於催化之理論國際研討會

(英文) 14

^th

International Conference on Theoretical Aspects of Catalysis (ICTAC-14)

發表論 文題目

Microkinetic Modeling of Ammonia Oxidation on RuO

2

(110)

Surfaces

conversion), K. Reuter (Towards a First-Principles Chemical Engineering) 等知名學 者敘述各種理論與方法的發展，及其對於催化反應的適用性。

P. Sautet (Tuning catalytic reactivity on metal and oxide surfaces: insights from DFT),

M. Neurock ( Catalytic Transformations of Biorenewable-Derived Oxygenates over

Acid and Base Sites on Supported Metal Particles), R. Catlow (Structure and

Mechanism in Microporous and Oxide Catalysis), X. Bao (Theoretical Aspect of

Catalysis with Nano-Confined Systems), M. Sprik (Redox Chemistry of Metal

Oxide-Water Interfaces) 等在不同催化體系或用途的研究，真的達到增廣見聞的

效果。

國科會補助計畫衍生研發成果推廣資料表

日期:2012/10/26

國科會補助計畫

計畫名稱: 理論計算對於小分子在觸媒上產氫之研究 計畫主持人: 江志強

計畫編號: 98-2113-M-011-001-MY3 學門領域: 物理化學

無研發成果推廣資料

98 年度專題研究計畫研究成果彙整表

計畫主持人：江志強 計畫編號：98-2113-M-011-001-MY3 計畫名稱：理論計算對於小分子在觸媒上產氫之研究

量化

成果項目

^{實際已達成}

數（被接受 或已發表）

預期總達成 數(含實際已

達成數)

本計畫實 際貢獻百

分比

單位

備 註

（

質 化 說 明：如 數 個 計 畫 共 同 成 果、成 果 列 為 該 期 刊 之 封 面 故 事 ...

等

）

期刊論文 0 0 100%

研究報告/技術報告

0 0 100%

研討會論文 0 0 100%

論文著作 篇

專書 0 0 100%

申請中件數 0 0 100%

專利 已獲得件數 0 0 100% 件

件數 0 0 100% 件

技術移轉

權利金 0 0 100% 千元

碩士生 9 9 100%

博士生 2 2 100%

博士後研究員 2 2 100%

國內

參與計畫人力

（本國籍）

專任助理 0 0 100%

人次

期刊論文 6 6 100%

研究報告/技術報告

0 0 100%

研討會論文 3 7 100%

篇

在國際會議中，不 包含壁報論文，除 了個人給予 3 次報 告外，我所指導的 學生亦參與 4 次口 頭報告。

論文著作

專書 0 0 100% 章/本

申請中件數 0 0 100%

專利 已獲得件數 0 0 100% 件

件數 0 0 100% 件

技術移轉

權利金 0 0 100% 千元

碩士生 0 0 100%

博士生 0 0 100%

博士後研究員 0 0 100%

國外

參與計畫人力

（外國籍）

專任助理 0 0 100%

人次

其他成果

( 無法以量化表達之成

果如辦理學術活動、獲 得獎項、重要國際合 作、研究成果國際影響 力及其他協助產業技 術發展之具體效益事 項等，請以文字敘述填 列。)

目前除已發表 以下幾篇論文外，Langmuir 2010, 26, 15845；J. Phys. Chem.

C 2010, 114, 18588；J. Phys. Chem. C 2011, 115, 516；J. Phys. Chem. C 2011, 115, 19203；Langmuir 2011, 27, 14253；J. Phys. Chem. C 2012, 116, 6367.

尚有 Hsin-Ni Chiang； J.C. Jiang*, ＇Density Functional Theory Study of Water-Gas-Shift Reaction on 3Cu/Al2O3(0001) Surface＇, (submit to J.

Catal.)； Vo Thanh Cong, Lam K. Huynh, J-Y. Hung and Jyh-Chaing Jiang*, ＇ Methanol Adsorption and Decomposition on ZnO Surface: A Density Functional Theory Study＇, (submit to J. Chem. Phys.)； Cong T. Vo, Lam K. Huynh,and Jyh-Chaing Jiang*, ＇CO Adsorption and Oxidation on Undoped and Ti-doped ZnO Surfaces: A Density Function Theory Study＇, (submit to J. Phys. Chem. C) 等論文投稿中。

成果項目 量化 名稱或內容性質簡述

測驗工具(含質性與量性)

0

課程/模組

0

電腦及網路系統或工具

0

教材

0

舉辦之活動/競賽

0

研討會/工作坊

0

電子報、網站

0

科 教 處 計 畫 加 填 項

目 計畫成果推廣之參與（閱聽）人數

0

國科會補助專題研究計畫成果報告自評表

請就研究內容與原計畫相符程度、達成預期目標情況、研究成果之學術或應用價 值（簡要敘述成果所代表之意義、價值、影響或進一步發展之可能性） 、是否適 合在學術期刊發表或申請專利、主要發現或其他有關價值等，作一綜合評估。

1. 請就研究內容與原計畫相符程度、達成預期目標情況作一綜合評估

■達成目標

□未達成目標（請說明，以 100 字為限）

□實驗失敗

□因故實驗中斷

□其他原因 說明：

2. 研究成果在學術期刊發表或申請專利等情形：

論文：■已發表 □未發表之文稿 □撰寫中 □無 專利：□已獲得 □申請中 ■無

技轉：□已技轉 □洽談中 ■無 其他：（以 100 字為限）

Langmuir 2010, 26, 15845.

J. Phys. Chem. C 2010, 114, 18588.

J. Phys. Chem. C 2011, 115, 516.

J. Phys. Chem. C 2011, 115, 19203.

Langmuir 2011, 27, 14253.

J. Phys. Chem. C 2012, 116, 6367.

3. 請依學術成就、技術創新、社會影響等方面，評估研究成果之學術或應用價 值（簡要敘述成果所代表之意義、價值、影響或進一步發展之可能性）（以 500 字為限）

除了已發表論文 6 篇外，另有 3 篇投稿到 JPCC、JCP 及 J Catal.等期刊，另有數篇撰寫

中。此 3 年計畫，我們在研究上的成果算是不錯，此計畫的研究過程，我們已建立研究異

相催化反應的技術，從吸附的研討中，藉由 DOS (density of states)及 EDD(electron

density difference)的分析，我們可以了解分子吸附的鍵結情形，更可預測可能的反應

機制，此亦有助於我們對於新催化劑的開發。此外，藉由此計畫的研究經驗，我已亦跨足

於 DSSC 方面的研究-染料吸附在半導體材料之電子耦合行為，具有設計 DSSC 的應用價值。