Effect of Additives on the Reactivity of Palladium Surfaces for the Chemisorption and Hydrogenation of Carbon Monoxide: A Surface Science and Catalytic Study - Thesis

Effect of Additives on the Reactivity of Palladium Surfaces for the Chemisorption and Hydrogenation of Carbon Monoxide: A Surface Science and Catalytic Study - 1987

Part 1	1	Introduction			1
		1.1	The Catalytic Hydrogenation of Carbon Monoxide		3
			1.1.1	Thermodynamics	3
			1.1.2	Metal-Oxide Systems	4
		1.2	Metal – Additives		7
		1.3	Perovskites		8
	2	Experimental			12
		2.1	Introduction		12
		2.2	Experimental Equipment		13
			2.2.1	Combined High-Pressure/Low Pressure Chamber	13
			2.2.2	Low Pressure Chamber	23
		2.3	Experimental Techniques		23
			2.3.1	Auger Electron Spectroscopy	25
			2.3.2	X-ray Photoelectron Spectroscopy	32
			2.3.3	Temperature Programmed Desorption	38
			2.3.4	Work Function	41
			2.3.5	Low Energy Electron Diffraction	42
		2.4	Experimental Procedure		46
			2.4.1	Surface Preparation	46
			2.4.2	UHV Experiments	49
			2.4.3	High Pressure Experiments	49
		2.5	Chemicals		50
	3	Palladium with Oxide Overlayers			53
		3.1	Introduction		53
		3.2	Results		55
			3.2.1	Auger Characterization	55
			3.2.2	CO Hydrogenation Activity	58
			3.2.3	CO Chemisorption	61
			3.2.4	XPS Characterization	66
			3.2.5	Work Function Measurements	79
		3.3	Discussion		79
			3.3.1	Oxide Growth and Diffusion	83
			3.3.2	Catalysis and Chemisorption	84
		3.4	Conclusions		91
Part 2	4	Palladium-Additives
		4.1	Introduction		96
		4.2	Results		97
			4.2.1	Pd(111) – Na, Si, P, S, Cl – CO	97
			4.2.2	Pd(111)- Si, P, S, Cl – H₂	101
			4.2.3	Pd(100) – K,Si, P, S, Cl – CO	101
			4.2.4	Pd(100) – Si, P, S, Cl-H₂	108
			4.2.5	Pd(110) – Na, Si, P, S, Cl – CO	109
			4.2.6	Pd(110) – Si, P, S, Cl – H₂	111
			4.2.7	Pd(100) – K, Si, O, S, Cl – Work Function	111
			4.2.8	LEED	115
			4.2.9	Pd(111) – S – CO (EELS)	115
			4.2.10	Pd – K, Si, P, S, Cl – C₂H₂	121
		4.3	Discussion		123
			4.3.1	Palladium – Additive Bonding	123
			4.3.2	CO Bonding on Clean Palladium	129
			4.3.3	The Effect of Additives on CO Bonding	130
			4.3.4	Effect of Additives on Hydrogen Bonding	140
			4.3.5	Palladium – Silicon	142
		4.4	Conclusions		143
	5	Perovskites			148
		5.1	Introduction		148
		5.2	Results and Discussion		150
			5.2.1	Introduction	150
			5.2.2	Catalytic Studies	151
			5.2.3	XPS Results	154
			5.2.4	LaRhO₃	155
		5.3	Conclusions		132
	6	Conclusions and Future Directions			165
	A	High Pressure Cell			169
	B	Curve Fitting Algorithm			181