原子团簇上一氧化碳的氧化

doi:10.7503/cjcu20131066

摘要/Abstract

摘要：

研究气态条件下原子团簇在完全可控、可重复条件下与CO的反应, 可以在分子水平上理解CO的氧化, 本综述对这些团簇研究工作进行了一些分析和总结, 讨论了团簇研究方法的特点、 CO氧化的新见解以及有待解决的问题.

Abstract:

Carbon monoxide binds to hemoglobin much more tightly than does molecular oxygen, so CO is highly toxic to humans and animals. Oxidation of CO into CO₂ is a major solution to removal of carbon monoxide in air purification. CO is also a simple molecule and CO oxidation serves as a prototypical reaction for heterogeneous processes. Atomic clusters composed of limited numbers of atoms are experimentally and theoretically tractable models for heterogeneous catalysis. During the last decade, a number of publications have been devoted to understanding the CO oxidation at a molecular level based on the investigations of gas phase atomic clusters under controlled and well reproducible conditions. In this review, we will go through the reported CO oxidations by gas phase atomic clusters. Advantages, new insights, and problems to be solved involved with the cluster approach for the title reaction will be summarized.

Key words: CO oxidation, Catalysis, Atomic cluster, Mass spectrometry, Density functional theory computation

中图分类号:

O641

TrendMD:

刘清宇, 何圣贵. 原子团簇上一氧化碳的氧化. 高等学校化学学报, 2014, 35(4): 665.

LIU Qingyu, HE Shenggui. Oxidation of Carbon Monoxide on Atomic Clusters^†. Chem. J. Chinese Universities, 2014, 35(4): 665.

图/表 17

Fig.1 Experimental setups used for studying the reactions between CO and atomic clustersPart (A) shows that a fast flow reactor is coupled with a laser ablation cluster source and a time-of-flight mass spectrometer in which a laser ionizes the neutral clusters, a mass gate selects cluster ions of interest, and a helium beam collides with the selected ions(adapted from refs.[33,42,45]). The reactor in (A) can be replaced by a quadrupole mass filter and a multi-pole(hexapole or octopole) collision cell(B, adapted from refs.[32,46]). The collision cell in (B) can be further replaced by an octopole ion trap(C, adapted from ref.[47]) and a Fourier-transform ion cyclotron resonance cell(D, adapted from refs.[49]). For (B) and (C), the ions coming out of the cell or trap are detected by a quadrupole[46] or a time-of-flight mass spectrometer[33].

Fig.2 Typical potential energy profile for CO oxidation on the MxOyq clusterThe reaction barrier and the binding energy between CO and MxOyq are indicated by variables Ea and Eb, respectively.

Fig.3 Calculated rates(A—C) and effective temperatures(D) for conversions of MxOyCOq into MxOy-1q+CO2(see Fig.2) The conversion rates with respect to the reaction barrier, the cluster vibrational temperature, and the number of atoms in the cluster are given in (A), (B) and (C), respectively. Eq.(2) in the text is used and the ν, Eb, and Ek are fixed at 3×1012 s-1, 1.5 eV, and 0.14 eV(a center-of-mass velocity of 1 km/s and a reduced mass of 28 amu), respectively. Other parameters fixed: T=298 K and x+y=10 for (A); Ea=1.0 eV and x+y=10 for (B); and Ea=1.0 eV and T=298 K for (C), in which the value denoted as bulk limit is calculated with Eq.(3) in the text. In (A), the ranges labeled as Ⅰ, Ⅱ, and Ⅲ represent the rates of energy dissipation(collision or infrared radiation) in the fast flow reactor[Fig.1(A)], in the collision cell and ion trap[Fig.1(B) and 1(C)], and in the FT-ICR cell[Fig.1(D)]. (D) shows the effective temperate(Teffective) at which the conversion rate of bulk limit(Eq.(3) with T=Teffective) equals to that of the cluster system in (C).

Table 1 Experimentally studied reactions between the oxide clusters MxOyq(q=0, ±1) and CO*

Species	Cluster			Product				k₁			Reactor		Remark			Year
Main	Al₂ $O 3 +$			Al₂ $O 2 +$ , Al₂O⁺, Al⁺				[1.4×10^-11]			B					2008^[57]
group	Al₂ $O 3 -$			Al₂ $O 2 -$				[ca.10^-14]			B					2008^[57]
	Al₂ $O 4 -$			Al₂ $O 3 -$				[4.6×10^-13]			B					2008^[57]
	CaO⁺			Ca⁺				2.5×10^-10			A					2005^[41]
	CaO⁺			Ca⁺				(2.8±1.5)×10^-10			A					2008^[58]
	GeO⁺			Ge⁺				2.1×10^-10			A					2005^[41]
	SrO⁺			Sr⁺				1.0×10^-10			A					2005^[41]
	BaO⁺			Ba⁺				2.3×10^-11			A					2005^[41]
d-Block	Sc₂ $O 4 -$			Sc₂ $O 3 -$				2.0×10^-10			A		Theory			2012^[30]
	Ti₂ $O 4 +$			Ti₂ $O 3 +$				[4.5×10^-12]			B		Theory			2011^[59]
	(TiO₂)_nO^-			(TiO₂ $) - n$				ca.10^-11			A		n=3—25, theory(n=3—8)			2013^[33]
	V₄ $O 10 +$			V₄ $O 9 +$				4.4×10^-11			B		Theory			2013^[32]
	VO₃			VO₂							A		Theory			2013^[34]
	Mn₂O₄			Mn₂O₃				6.5×10^-13			A		Theory			2013^[38]
	Mn₃O₇			Mn₃O₆				1.9×10^-13			A		Theory			2013^[38]
	FeO⁺			Fe⁺				9×10^-10			D					1981^[60]
	FeO⁺			Fe⁺				1.8×10^-10			A		Theory			2005^[41]
	FeO(N₂O $) n +$			Fe⁺				ca.10^-10			A		n=0—3			1995^[92]
	Fe $O 2 +$			FeO⁺, FeCO⁺				[5.3×10^-12]			B		Theory			2007^[61]
	Fe $O 3 +$			FeO⁺, FeOCO⁺, Fe⁺							B					2007^[61]
	Fe $O 3 +$			Fe $O 2 +$ , FeO⁺, FeOCO⁺, Fe⁺				[1.4×10^-12]			B					2007^[62]
	Fe $O 4 +$			FeO₂CO⁺, Fe(CO $) 2 +$ , FeO⁺				[5.5×10^-12]			B		Loss of molecular O₂, theory			2007^[61]
	Fe $O 5 +$			Fe $O 3 +$ , FeO₃CO⁺							B					2007^[61]
	Fe₂O⁺			F $e 2 +$							B		Theory			2007^[61]
	Fe₂ $O 2 +$			Fe₂O⁺, F $e 2 +$ , Fe₂CO⁺				[8.8×10^-13]			B		Theory			2007^[61]
	Fe₂ $O 3 +$			Fe₂ $O 2 +$				[ca.10^-13]			B					2007^[61]
	Fe₂ $O 4 +$			Fe₂O₂CO⁺, Fe₂ $O 2 +$							B		Theory			2007^[61]
	Fe₂ $O 5 +$			Fe₂ $O 3 +$ , Fe₂O₃CO⁺,							B		Theory			2007^[61]
				Fe₂ $O 2 +$
	FeO₂			FeO				5.3×10^-12			A		Theory			2008^[43]
	FeO₃			FeO₂				1.3×10^-12			A		Theory			2008^[43]
	Fe $O 2 -$			FeO^-							B					2007^[63]
	Fe $O 2 -$			FeO^-				1.9×10^-12			B		Theory			2010^[64]
	Fe $O 3 -$			Fe $O 2 -$				[ca.10^-14]			B					2007^[62]
	Fe $O 3 -$			Fe $O 2 -$							B					2007^[63]
	Fe $O 4 -$			Fe $O 2 -$ , Fe $O 3 -$				[2.9×10^-13]			B		Loss of molecular O₂ and			2007^[63]
													CO oxidation
Species	Cluster		Product			k₁			Reactor			Remark		Year
d-Block	Fe₂ $O 3 -$		Fe₂ $O 2 -$						B					2007^[63]
	Fe₂ $O 3 -$		Fe₂ $O 2 -$			1.8×10^-12			B					2010^[64]
	Fe₂ $O 4 -$		Fe₂ $O 3 -$ , Fe $O 3 -$						B					2007^[63]
	Fe₂ $O 5 -$		Fe₂ $O 4 -$ , Fe $O 3 -$						B					2007^[63]
	Fe₂ $O 6 -$		Fe₂ $O 5 -$ , Fe₂ $O 4 -$			[4.5×10^-13]			B			Loss of molecular O₂ and		2007^[63]
												CO oxidation
	CoO⁺		Co⁺						B					2008^[66]
	Co $O 2 +$		Co⁺, CoCO⁺			[9.3×10^-12]			B			Loss of molecular O₂,theory		2008^[66]
	Co $O 3 +$		CoO⁺, CoOCO⁺, Co⁺			[7.2×10^-12]			B			Loss of molecular O₂		2008^[66]
	Co $O 4 +$		Co $O 2 +$ , CoO₂CO⁺ , Co(CO $) 1,2 +$						B			Loss of molecular O₂		2008^[66]
	Co₂ $O 2 +$		CoO₂CO⁺ , Co(CO $) 2 +$			[1.3×10^-12]			B			Loss of molecular O₂,		2008^[66]
												cluster fragmentation
	Co₂ $O 4 +$		Co₂ $O 2 +$ , Co₂CO⁺,			[4.7×10^-12]			B			Loss of molecular O₂		2008^[66]
			CoO₂CO⁺, Co(CO $) 2 +$
	Co₂ $O 6 +$		Co₂ $O 4 +$ , Co₂ $O 2 +$ , Co(CO $) 2 +$						B			Loss of molecular O₂		2008^[66]
	Co_nO_m		Co_n $O m - 1$			10^-13—10^-12			A			n=3—9, m=3—13,		2010^[65]
												theory(Co₃O₄)
	Co $O 2 -$		CoO^-						B					2008^[66]
	Co $O 2 -$		CoO^-			0.3×10^-12			B					2010^[64]
	Co $O 3 -$		Co $O 2 -$						B					2008^[66]
	Co₂ $O 3 -$		Co₂ $O 2 -$ , Co $O 2 -$						B					2008^[66]
	Co₂ $O 3 -$		Co₂ $O 2 -$			1.6×10^-12			B					2010^[64]
	Co₂ $O 5 -$		Co₂ $O 4 -$ , Co₂ $O 3 -$ , Co $O 3 -$			[4.8×10^-14]			B					2008^[66]
	Co₃ $O 5 -$		Co₃ $O 4 -$ , Co₃ $O 3 -$			[1.4×10^-13]			B					2008^[66]
	Co₃ $O 6 -$		Co₃ $O 5 -$ , Co₃ $O 4 -$ , Co₃ $O 3 -$ ,			[1.0×10^-13]			B					2008^[66]
			Co₂ $O 4 -$ , Co₂ $O 3 -$
	Ni₆ $O 7 +$		Ni₆ $O 6 +$			2.2×10^-13			A					2013^[37]
	Ni₈ $O 9 +$		Ni₈ $O 8 +$			1.2×10^-13			A					2013^[37]
	Ni $O 2 -$		NiO^-			(9.2±0.5)×10^-14			B					2009^[67]
	Ni $O 2 -$		NiO^-			0.4×10^-12			B					2010^[64]
	Ni $O 3 -$		Ni $O 2 -$						B					2009^[67]
	Ni₂ $O 3 -$		Ni₂ $O 2 -$ , Ni $O 2 -$			(1.9±0.1)×10^-13			B					2009^[67]
	Ni₂ $O 3 -$		Ni₂ $O 2 -$			1.0×10^-12			B					2010^[64]
	Ni₃ $O 4 -$		Ni₃ $O 3 -$			(9.6±0.8)×10^-14			B					2009^[67]
	Ni₄ $O 5 -$		Ni₄ $O 4 -$ , Ni₄ $O 3 -$			(3.0±0.2)×10^-13			B					2009^[67]
	Cu $O 2 -$		CuO^-			0.7×10^-12			B					2010^[64]
	Cu₂ $O 3 -$		Cu₂ $O 2 -$			1.5×10^-12			B					2010^[64]
	Cu₅ $O 2 -$		Cu₅O^-						B					2013^[36]
	Cu₉ $O 2 -$		Cu₉O^-						B					2013^[36]
	Zr₂ $O 4 +$		Zr₂ $O 3 +$			1.8×10^-10			A					2010^[27]
	(ZrO₂ $) n +$		Zr_n $O 2 n - 1 +$			2.4×10^-12, 1.6×10^-12,			B			n=1—5, k₁ for		2008^[68]
						1.2×10^-12, 6.3×10^-13						n=2—5,theory
	(ZrO₂)_nO^-		(ZrO₂ $) n -$			2.1×10^-12, 2.2×10^-13,			B			n=1—4, theory		2009^[69]
						3.4×10^-13, 1.8×10^-13
	(ZrO₂)_nO^-		(ZrO₂)_nC $O 2 -$			ca.10^-11			A			n=3—25, Oxidative adsorption		2013^[33]
	Mo $O n -$		Mo(CO $) 5 -$ , MoO(CO $) 3 -$ ,						A			n=1—3		2006^[70]
			C₆ $O 6 -$											2007^[71]
	Rh_nO_m		Rh_n $O m - 1$			ca.10^-10			A			n=10—28, m=1—5,		2012^[35]
												k₁ for m=4, 5
	Pd $O 2 +$		PdO⁺, OPdCO⁺, PdCO⁺						B			Loss of molecular O₂ and		2011^[72]
												CO oxidation, theory
	Pd $O 3 +$		Pd $O 2 +$ , O₂PdCO⁺,						B			Loss of molecular O₂ and		2011^[72]
			OPdCO⁺									CO oxidation, theory
	Pd_nO⁺		Pd_n(CO $) x +$						C			n=2—7		2012^[26]
	Pd_n $O 2 +$		Pd_n(CO $) x +$						C			n=4—6		2012^[26]
Species		Cluster			Product		k₁			Reactor		Remark			Year
d-Block		Pd₆ $O 4 +$			Pd₆ $O 3 +$					C		Theory			2012^[25]
		Pd₆ $O 5 +$			Pd₆O₅CO⁺					C		Eliminate CO₂ and form			2012^[25]
												Pd₆ $O 4 +$ rapidly, theory
		Ag₃ $O n +$			Ag₃O_n(OCO $) n +$					C		n=1—3, with N₂O			2011^[73]
		Ag_n $O 4 -$			A $g n -$					C		n=7, 9, 11			2004^[74]
		Ag₅ $O 4 -$			Ag₄ $O 6 -$ , Ag₃ $O 4 -$ ,					C		Cluster fragmentation			2005^[75]
					Ag₃C $O 2 -$ , A $g 3 -$
		Ag_nN_x $O - y$			Ag₃NO^-, AgN₂ $O 4 -$					C		n=2—5, y>x, cluster			2007^[76]
												fragmentation
		La₂ $O 4 -$			La₂O₃+e^-		1.9×10^-10			A		Electron detachment, theory			2012^[30]
		W_n $O 3 n +$			W_n $O 3 n - 1 +$		3.0×10^-12, 3.6×10^-13,			B		n=1—3			2008^[77]
							5.9×10^-13
		Re $O 3 +$			Re $O 2 +$		3.3×10^-10			D					2001^[78]
		Re $O 4 +$			Re $O 3 +$		2.4×10^-10			D					2001^[78]
		Os $O n +$			Os $O n - 1 +$		≥4.0×10^-13			A		n=1—4, k₁ for n=1			2005^[41]
		Ir $O n +$			Ir $O n - 1 +$		3.5×10^-10			A		n=1—3, k₁ for n=1			2005^[41]
		Pt $O 2 +$			PtO⁺, Pt⁺		6.6×10^-10			D					2001^[79]
		Pt $O n +$			Pt $O n - 1 +$		2.3×10^-10			A		n=1—3, k₁ for n=1			2005^[41]
		Pt₇ $O n +$			Pt₇ $O n - 1 +$		ca.10^-9			D		n=1—2			2004^[80]
		Pt₄ $O n -$			Pt₄ $O n - 1 -$		10^-11—10^-9			D		n=1—3, 4(slow)			2007^[81]
		Pt_n $O - m$			Pt_n $O - m - 1$					B		n=3—6, m=1—2			1998^[82]
		AuO⁺			AuCO⁺					B		Theory			2008^[89]
		AuO⁺			AuCO⁺		7.93×10^-12			B					2008^[90]
		Au₂O⁺			Au₂CO⁺					B		Theory			2008^[89]
		Au₂O⁺			Au₂CO⁺		2.42×10^-12			B					2008^[90]
		Au₃O⁺			Au₃CO⁺		4.98×10^-12			B					2008^[90]
		Au₃ $O 3 +$			Au₃(CO₂ $) 3 +$ , Au₃(CO $) 3 +$					C					2011^[73]
		Au_n $O m +$			Au_nO_x(CO $) y +$					A		n=1—2, m=1—5,			2004^[88]
												x=0—3, y=0—2
		AuO^-			Au^-		ca.10^-11			A		Theory			2004^[83]
		Au $O 2 -$			AuO^-					A		Very slow, theory			2004^[83]
		Au $O 3 -$			Au^-		ca.10^-12			A		Slow, loss of molecular O₂,			2004^[83]
												theory
		Au₂O^-			A $u 2 -$		ca.10^-13			A		Theory			2006^[84],2007^[86]
		Au₂ $O 2 -$			A $u 2 -$					B					2003^[87]
		Au₂ $O 2 -$			A $u 2 -$					C					2005^[75]
		Au₂ $O 2 -$			A $u 2 -$					A		Theory			2006^[84]
		Au₂ $O 3 -$			Au₂ $O 2 -$ , Au₂O^-		ca.10^-13			A		Theory			2006^[84]
		Au₂ $O 4 -$			Au₂ $O 3 -$ , Au₂ $O 2 -$		ca.10^-13			A		Theory			2006^[84]
		Au₆ $O 2 -$			Au₆O^-, A $u 6 -$					A		CO and O₂ co-adsorption			2002^[50]
		Au_n $O - m$			Au_xO_y(CO $) - z$					A		n ≥ 4, Oxidation, replacement			2006^[85]
												and association
f-Block		Ce_n $O 2 n +$			Ce_n $O 2 n - 1 +$		1.9×10^-12			A		n=2—6, k₁ for Ce₂ $O 4 +$ ,			2010^[27]
												theory(n =2—5)
		Ce_n $O 2 n + 1 -$			Ce_n $O 2 n -$		8×10^-11			A		n=4—21, k₁ for Ce₄ $O 9 -$ ,			2011^[28]
												theory(n =1—6)
		EuO⁺			Eu⁺		≥3.3×10^-12			A					2005^[41]
		YbO⁺			Yb⁺		1.2×10^-11			A					2005^[41]
Hetero-		AlV $O 4 +$			AlV $O 3 +$		4.1×10^-10			D		Theory			2011^[91]
nuclear		VCoO₄			VCoO₃		ca.10^-11			A		Theory			2012^[29]
		YAl $O 3 +$			YAl $O 2 +$					D		Theory			2013^[31]
		AuTi₃ $O 6 +$			AuTi₃O₆CO⁺					A		Molecular association			2011^[40]

Table 1 Experimentally studied reactions between the oxide clusters MxOyq(q=0, ±1) and CO*

Species	Cluster			Product				k₁			Reactor		Remark			Year
Main	Al₂ $O 3 +$			Al₂ $O 2 +$ , Al₂O⁺, Al⁺				[1.4×10^-11]			B					2008^[57]
group	Al₂ $O 3 -$			Al₂ $O 2 -$				[ca.10^-14]			B					2008^[57]
	Al₂ $O 4 -$			Al₂ $O 3 -$				[4.6×10^-13]			B					2008^[57]
	CaO⁺			Ca⁺				2.5×10^-10			A					2005^[41]
	CaO⁺			Ca⁺				(2.8±1.5)×10^-10			A					2008^[58]
	GeO⁺			Ge⁺				2.1×10^-10			A					2005^[41]
	SrO⁺			Sr⁺				1.0×10^-10			A					2005^[41]
	BaO⁺			Ba⁺				2.3×10^-11			A					2005^[41]
d-Block	Sc₂ $O 4 -$			Sc₂ $O 3 -$				2.0×10^-10			A		Theory			2012^[30]
	Ti₂ $O 4 +$			Ti₂ $O 3 +$				[4.5×10^-12]			B		Theory			2011^[59]
	(TiO₂)_nO^-			(TiO₂ $) - n$				ca.10^-11			A		n=3—25, theory(n=3—8)			2013^[33]
	V₄ $O 10 +$			V₄ $O 9 +$				4.4×10^-11			B		Theory			2013^[32]
	VO₃			VO₂							A		Theory			2013^[34]
	Mn₂O₄			Mn₂O₃				6.5×10^-13			A		Theory			2013^[38]
	Mn₃O₇			Mn₃O₆				1.9×10^-13			A		Theory			2013^[38]
	FeO⁺			Fe⁺				9×10^-10			D					1981^[60]
	FeO⁺			Fe⁺				1.8×10^-10			A		Theory			2005^[41]
	FeO(N₂O $) n +$			Fe⁺				ca.10^-10			A		n=0—3			1995^[92]
	Fe $O 2 +$			FeO⁺, FeCO⁺				[5.3×10^-12]			B		Theory			2007^[61]
	Fe $O 3 +$			FeO⁺, FeOCO⁺, Fe⁺							B					2007^[61]
	Fe $O 3 +$			Fe $O 2 +$ , FeO⁺, FeOCO⁺, Fe⁺				[1.4×10^-12]			B					2007^[62]
	Fe $O 4 +$			FeO₂CO⁺, Fe(CO $) 2 +$ , FeO⁺				[5.5×10^-12]			B		Loss of molecular O₂, theory			2007^[61]
	Fe $O 5 +$			Fe $O 3 +$ , FeO₃CO⁺							B					2007^[61]
	Fe₂O⁺			F $e 2 +$							B		Theory			2007^[61]
	Fe₂ $O 2 +$			Fe₂O⁺, F $e 2 +$ , Fe₂CO⁺				[8.8×10^-13]			B		Theory			2007^[61]
	Fe₂ $O 3 +$			Fe₂ $O 2 +$				[ca.10^-13]			B					2007^[61]
	Fe₂ $O 4 +$			Fe₂O₂CO⁺, Fe₂ $O 2 +$							B		Theory			2007^[61]
	Fe₂ $O 5 +$			Fe₂ $O 3 +$ , Fe₂O₃CO⁺,							B		Theory			2007^[61]
				Fe₂ $O 2 +$
	FeO₂			FeO				5.3×10^-12			A		Theory			2008^[43]
	FeO₃			FeO₂				1.3×10^-12			A		Theory			2008^[43]
	Fe $O 2 -$			FeO^-							B					2007^[63]
	Fe $O 2 -$			FeO^-				1.9×10^-12			B		Theory			2010^[64]
	Fe $O 3 -$			Fe $O 2 -$				[ca.10^-14]			B					2007^[62]
	Fe $O 3 -$			Fe $O 2 -$							B					2007^[63]
	Fe $O 4 -$			Fe $O 2 -$ , Fe $O 3 -$				[2.9×10^-13]			B		Loss of molecular O₂ and			2007^[63]
													CO oxidation
Species	Cluster		Product			k₁			Reactor			Remark		Year
d-Block	Fe₂ $O 3 -$		Fe₂ $O 2 -$						B					2007^[63]
	Fe₂ $O 3 -$		Fe₂ $O 2 -$			1.8×10^-12			B					2010^[64]
	Fe₂ $O 4 -$		Fe₂ $O 3 -$ , Fe $O 3 -$						B					2007^[63]
	Fe₂ $O 5 -$		Fe₂ $O 4 -$ , Fe $O 3 -$						B					2007^[63]
	Fe₂ $O 6 -$		Fe₂ $O 5 -$ , Fe₂ $O 4 -$			[4.5×10^-13]			B			Loss of molecular O₂ and		2007^[63]
												CO oxidation
	CoO⁺		Co⁺						B					2008^[66]
	Co $O 2 +$		Co⁺, CoCO⁺			[9.3×10^-12]			B			Loss of molecular O₂,theory		2008^[66]
	Co $O 3 +$		CoO⁺, CoOCO⁺, Co⁺			[7.2×10^-12]			B			Loss of molecular O₂		2008^[66]
	Co $O 4 +$		Co $O 2 +$ , CoO₂CO⁺ , Co(CO $) 1,2 +$						B			Loss of molecular O₂		2008^[66]
	Co₂ $O 2 +$		CoO₂CO⁺ , Co(CO $) 2 +$			[1.3×10^-12]			B			Loss of molecular O₂,		2008^[66]
												cluster fragmentation
	Co₂ $O 4 +$		Co₂ $O 2 +$ , Co₂CO⁺,			[4.7×10^-12]			B			Loss of molecular O₂		2008^[66]
			CoO₂CO⁺, Co(CO $) 2 +$
	Co₂ $O 6 +$		Co₂ $O 4 +$ , Co₂ $O 2 +$ , Co(CO $) 2 +$						B			Loss of molecular O₂		2008^[66]
	Co_nO_m		Co_n $O m - 1$			10^-13—10^-12			A			n=3—9, m=3—13,		2010^[65]
												theory(Co₃O₄)
	Co $O 2 -$		CoO^-						B					2008^[66]
	Co $O 2 -$		CoO^-			0.3×10^-12			B					2010^[64]
	Co $O 3 -$		Co $O 2 -$						B					2008^[66]
	Co₂ $O 3 -$		Co₂ $O 2 -$ , Co $O 2 -$						B					2008^[66]
	Co₂ $O 3 -$		Co₂ $O 2 -$			1.6×10^-12			B					2010^[64]
	Co₂ $O 5 -$		Co₂ $O 4 -$ , Co₂ $O 3 -$ , Co $O 3 -$			[4.8×10^-14]			B					2008^[66]
	Co₃ $O 5 -$		Co₃ $O 4 -$ , Co₃ $O 3 -$			[1.4×10^-13]			B					2008^[66]
	Co₃ $O 6 -$		Co₃ $O 5 -$ , Co₃ $O 4 -$ , Co₃ $O 3 -$ ,			[1.0×10^-13]			B					2008^[66]
			Co₂ $O 4 -$ , Co₂ $O 3 -$
	Ni₆ $O 7 +$		Ni₆ $O 6 +$			2.2×10^-13			A					2013^[37]
	Ni₈ $O 9 +$		Ni₈ $O 8 +$			1.2×10^-13			A					2013^[37]
	Ni $O 2 -$		NiO^-			(9.2±0.5)×10^-14			B					2009^[67]
	Ni $O 2 -$		NiO^-			0.4×10^-12			B					2010^[64]
	Ni $O 3 -$		Ni $O 2 -$						B					2009^[67]
	Ni₂ $O 3 -$		Ni₂ $O 2 -$ , Ni $O 2 -$			(1.9±0.1)×10^-13			B					2009^[67]
	Ni₂ $O 3 -$		Ni₂ $O 2 -$			1.0×10^-12			B					2010^[64]
	Ni₃ $O 4 -$		Ni₃ $O 3 -$			(9.6±0.8)×10^-14			B					2009^[67]
	Ni₄ $O 5 -$		Ni₄ $O 4 -$ , Ni₄ $O 3 -$			(3.0±0.2)×10^-13			B					2009^[67]
	Cu $O 2 -$		CuO^-			0.7×10^-12			B					2010^[64]
	Cu₂ $O 3 -$		Cu₂ $O 2 -$			1.5×10^-12			B					2010^[64]
	Cu₅ $O 2 -$		Cu₅O^-						B					2013^[36]
	Cu₉ $O 2 -$		Cu₉O^-						B					2013^[36]
	Zr₂ $O 4 +$		Zr₂ $O 3 +$			1.8×10^-10			A					2010^[27]
	(ZrO₂ $) n +$		Zr_n $O 2 n - 1 +$			2.4×10^-12, 1.6×10^-12,			B			n=1—5, k₁ for		2008^[68]
						1.2×10^-12, 6.3×10^-13						n=2—5,theory
	(ZrO₂)_nO^-		(ZrO₂ $) n -$			2.1×10^-12, 2.2×10^-13,			B			n=1—4, theory		2009^[69]
						3.4×10^-13, 1.8×10^-13
	(ZrO₂)_nO^-		(ZrO₂)_nC $O 2 -$			ca.10^-11			A			n=3—25, Oxidative adsorption		2013^[33]
	Mo $O n -$		Mo(CO $) 5 -$ , MoO(CO $) 3 -$ ,						A			n=1—3		2006^[70]
			C₆ $O 6 -$											2007^[71]
	Rh_nO_m		Rh_n $O m - 1$			ca.10^-10			A			n=10—28, m=1—5,		2012^[35]
												k₁ for m=4, 5
	Pd $O 2 +$		PdO⁺, OPdCO⁺, PdCO⁺						B			Loss of molecular O₂ and		2011^[72]
												CO oxidation, theory
	Pd $O 3 +$		Pd $O 2 +$ , O₂PdCO⁺,						B			Loss of molecular O₂ and		2011^[72]
			OPdCO⁺									CO oxidation, theory
	Pd_nO⁺		Pd_n(CO $) x +$						C			n=2—7		2012^[26]
	Pd_n $O 2 +$		Pd_n(CO $) x +$						C			n=4—6		2012^[26]
Species		Cluster			Product		k₁			Reactor		Remark			Year
d-Block		Pd₆ $O 4 +$			Pd₆ $O 3 +$					C		Theory			2012^[25]
		Pd₆ $O 5 +$			Pd₆O₅CO⁺					C		Eliminate CO₂ and form			2012^[25]
												Pd₆ $O 4 +$ rapidly, theory
		Ag₃ $O n +$			Ag₃O_n(OCO $) n +$					C		n=1—3, with N₂O			2011^[73]
		Ag_n $O 4 -$			A $g n -$					C		n=7, 9, 11			2004^[74]
		Ag₅ $O 4 -$			Ag₄ $O 6 -$ , Ag₃ $O 4 -$ ,					C		Cluster fragmentation			2005^[75]
					Ag₃C $O 2 -$ , A $g 3 -$
		Ag_nN_x $O - y$			Ag₃NO^-, AgN₂ $O 4 -$					C		n=2—5, y>x, cluster			2007^[76]
												fragmentation
		La₂ $O 4 -$			La₂O₃+e^-		1.9×10^-10			A		Electron detachment, theory			2012^[30]
		W_n $O 3 n +$			W_n $O 3 n - 1 +$		3.0×10^-12, 3.6×10^-13,			B		n=1—3			2008^[77]
							5.9×10^-13
		Re $O 3 +$			Re $O 2 +$		3.3×10^-10			D					2001^[78]
		Re $O 4 +$			Re $O 3 +$		2.4×10^-10			D					2001^[78]
		Os $O n +$			Os $O n - 1 +$		≥4.0×10^-13			A		n=1—4, k₁ for n=1			2005^[41]
		Ir $O n +$			Ir $O n - 1 +$		3.5×10^-10			A		n=1—3, k₁ for n=1			2005^[41]
		Pt $O 2 +$			PtO⁺, Pt⁺		6.6×10^-10			D					2001^[79]
		Pt $O n +$			Pt $O n - 1 +$		2.3×10^-10			A		n=1—3, k₁ for n=1			2005^[41]
		Pt₇ $O n +$			Pt₇ $O n - 1 +$		ca.10^-9			D		n=1—2			2004^[80]
		Pt₄ $O n -$			Pt₄ $O n - 1 -$		10^-11—10^-9			D		n=1—3, 4(slow)			2007^[81]
		Pt_n $O - m$			Pt_n $O - m - 1$					B		n=3—6, m=1—2			1998^[82]
		AuO⁺			AuCO⁺					B		Theory			2008^[89]
		AuO⁺			AuCO⁺		7.93×10^-12			B					2008^[90]
		Au₂O⁺			Au₂CO⁺					B		Theory			2008^[89]
		Au₂O⁺			Au₂CO⁺		2.42×10^-12			B					2008^[90]
		Au₃O⁺			Au₃CO⁺		4.98×10^-12			B					2008^[90]
		Au₃ $O 3 +$			Au₃(CO₂ $) 3 +$ , Au₃(CO $) 3 +$					C					2011^[73]
		Au_n $O m +$			Au_nO_x(CO $) y +$					A		n=1—2, m=1—5,			2004^[88]
												x=0—3, y=0—2
		AuO^-			Au^-		ca.10^-11			A		Theory			2004^[83]
		Au $O 2 -$			AuO^-					A		Very slow, theory			2004^[83]
		Au $O 3 -$			Au^-		ca.10^-12			A		Slow, loss of molecular O₂,			2004^[83]
												theory
		Au₂O^-			A $u 2 -$		ca.10^-13			A		Theory			2006^[84],2007^[86]
		Au₂ $O 2 -$			A $u 2 -$					B					2003^[87]
		Au₂ $O 2 -$			A $u 2 -$					C					2005^[75]
		Au₂ $O 2 -$			A $u 2 -$					A		Theory			2006^[84]
		Au₂ $O 3 -$			Au₂ $O 2 -$ , Au₂O^-		ca.10^-13			A		Theory			2006^[84]
		Au₂ $O 4 -$			Au₂ $O 3 -$ , Au₂ $O 2 -$		ca.10^-13			A		Theory			2006^[84]
		Au₆ $O 2 -$			Au₆O^-, A $u 6 -$					A		CO and O₂ co-adsorption			2002^[50]
		Au_n $O - m$			Au_xO_y(CO $) - z$					A		n ≥ 4, Oxidation, replacement			2006^[85]
												and association
f-Block		Ce_n $O 2 n +$			Ce_n $O 2 n - 1 +$		1.9×10^-12			A		n=2—6, k₁ for Ce₂ $O 4 +$ ,			2010^[27]
												theory(n =2—5)
		Ce_n $O 2 n + 1 -$			Ce_n $O 2 n -$		8×10^-11			A		n=4—21, k₁ for Ce₄ $O 9 -$ ,			2011^[28]
												theory(n =1—6)
		EuO⁺			Eu⁺		≥3.3×10^-12			A					2005^[41]
		YbO⁺			Yb⁺		1.2×10^-11			A					2005^[41]
Hetero-		AlV $O 4 +$			AlV $O 3 +$		4.1×10^-10			D		Theory			2011^[91]
nuclear		VCoO₄			VCoO₃		ca.10^-11			A		Theory			2012^[29]
		YAl $O 3 +$			YAl $O 2 +$					D		Theory			2013^[31]
		AuTi₃ $O 6 +$			AuTi₃O₆CO⁺					A		Molecular association			2011^[40]

Fig.4 DFT calculated reaction pathway for Ti3O7-+CO→Ti3O6-+CO2[33]The zero-point vibration corrected energies(DH0K/eV) of the reaction intermediates(IM1—IM3), transition states(TS1 and TS2), and products(Ti3O6-+CO2) with respect to the separated reactants(Ti3O7-+CO) are given. Bond lengths in pm are shown.

Fig.5 DFT calculated reaction pathway for Co3O4+CO→Co3O3+CO2[65]The zero-point vibration corrected energies(DH0 K/eV) of the reaction intermediates(IM4 and IM5), transition state(TS3), and products(Co3O3+CO2) with respect to the separated reactants(Co3O4+CO) are given. Bond lengths in pm are shown.

Fig.6 DFT calculated reaction pathway for Au2O2-+2CO→Au2-+2CO2[84] The zero-point vibration corrected energies(DH0 K/eV) of the reaction intermediates(IM6—IM9), transition states(TS4—TS6), and products(Au2-+2CO2) with respect to the separated reactants(Au2O2-+2CO) are given. Bond lengths in pm are shown.

Fig.7 Experimentally determined relative pseudo-first order rate constants(k1) for(CeO2)nO-+CO→ (CeO2)n-+CO2(n=4—21)(A) and DFT calculated structures and profiles of unpaired spin density distributions for(CeO2)nO-(n=1—6) clusters(B)[28] The experiment identified no evidence of reaction between(CeO2)nO-(n=1—3) and CO, so the rate constants are simply set to be zero. The absolute values of k1(Ce4O9-+CO) under the conditions of 0.3 and 1.0 Pa CO in the fast flow reactor are 8.6×10-11 and 7.8×10-11 cm3·molecule-1·s-1, respectively. Abundance of un-reactive cluster isomers can lead to the result that the rate constants under the condition of 0.3 Pa are generally larger than those under 1.0 Pa. The spin density values over oxygen atoms in μB and some Ce—O bond lengths in pm are shown.

Fig.8 TOF mass spectra for reactions of Ti5Oy-(A—D) and Zr4Oy-(E—H) with CO in the fast flow reactor[33]The numbers x, y denote MxO-y in which M=Ti or Zr. The simulated Ti5O11- and Zr4O9- isotopomers are given in (A) and (E). The reference spectra with N2 in the reactor are given in (B) and(F). The spectra with 1.4 and 0.6 Pa CO in the reactor are given in (C) and (G), respectively. The difference spectra[(D)=(C)-(B) and (H)=(G)-(F)] are also shown.

Fig.9 Simplified potential energy profiles for oxidative CO absorption and CO2 desorption in the reactions of CO with M8O17-(M=Ti, Zr) calculated by the DFT[33]The zero-point vibration corrected energies(DH0 K/eV) of the reaction intermediates(1 and 1') and products(4 and 4') with respect to the separated reactants are given. The energies of 2/3 and 2'/3' are calculated with the geometric parameters of M8O16 being fixed at the values of the M8O16 moiety in 1 and 1', respectively(EA denotes electron affinity in eV). Bond lengths in pm are shown.

Fig.10 Proposed catalytic cycles involving O2- and O- radicals for low-temperature CO oxidation over titania and zirconia supported gold[33] Gold may participate in the O—O bond activation because it was identified that O2- is unable to react with CO in the absence of gold at low-temperature[103,136,137].

Fig.11 B3LYP/6-311+G* calculated reaction pathways for FeO2q+CO→FeOq+CO2 in which q=+1(A), 0(B) and -1(C)The zero-point vibration corrected energies(ΔH0 K/eV) of the reaction intermediates(IM10—IM16), transition states(TS7—TS10), and products(FeOq+CO2) with respect to the separated reactants(FeO2q+CO) are given. Bond lengths in pm are shown. The structures and mechanisms of FeO2+, FeO2, and FeO2- reaction systems are adapted from refs.[61], [43], and [63], respectively.

Fig.12 Three model catalytic cycles Ⅰ—Ⅲ for CO oxidation by O2 over FeO1—3 and Fe2O2—5 clusters[43] The free energy barrier(eV) of the rate-limiting step in each elementary reaction is given.

Fig.13 Concentration of all product ions observed during the reactions of mass selected Au2- with CO and O2 inside the octopole ion trap as a function of the reaction time(tR) for different CO partial pressures[87] (A) p(CO)=0 and p(O2)=0.12 Pa, (B) p(CO)=p(O2)=0.12 Pa, (C) p(CO)=2p(O2)=0.24 Pa. The reaction temperature and bath gas(He) pressure are 300 K and 1.2 Pa, respectively.

Fig.14 DFT calculated potential energy profile for direct and catalytic oxidations of CO by N2O[91]Catalysts=AlVO3+ and AlVO4+. The energies of the intermediates(IM17—IM19), transition states(TS11 and TS12), and products with respect to the separated reactants are expressed in eV. Bond lengths in pm are shown.

Table 2 Experimentally studied catalytic oxidations of CO on atomic cluster catalysts

Catalyst	Oxidant	Reactor	Remark	Year
Al₂ $O 2 +$ , Al₂ $O 3 +$	N₂O	B		2008^[57]
Al₂ $O 2 — 4 -$	N₂O	B		2008^[57]
Ca⁺, CaO⁺	N₂O	A		2005^[41]
Ti₂ $O 3 +$ , Ti₂ $O 4 +$	N₂O	B	Theory	2011^[59]
VO₂, VO₃	N₂O	A	Theory	2013^[34]
Mn₂O₄, Mn₂O₅	NO₂	A	Theory	2013^[38]
Fe⁺, FeO⁺	N₂O	D		1981^[60]
Fe⁺, FeO⁺	N₂O	A	Theory	2005^[41]
Ge⁺, GeO⁺	N₂O	A		2005^[41]
Sr⁺, SrO⁺	N₂O	A		2005^[41]
Zr_n $O + 2 n - 1$ , Zr_n $O 2 n +$	N₂O	B	n=1—4, theory	2008^[68]
Rh_nO_m	N₂O	A	n=10—28, m=0—5	2011^[35]
Pd₆ $O 3 — 5 +$	O₂	C	Theory	2012^[25]
A $g n -$ , Ag_n $O 4 -$	O₂	C	n=7, 9, 11	2004^[74]
Ba⁺, BaO⁺	N₂O	A		2005^[41]
Eu⁺, EuO⁺	N₂O	A		2005^[41]
Yb⁺, YbO⁺	N₂O	A		2005^[41]
Os $O 0 — 4 +$	N₂O	A		2005^[41]
Ir $O 0 — 3 +$	N₂O	A		2005^[41]
Pt $O 0 — 3 +$	N₂O	A		2005^[41]
Pt⁺, Pt $O 2 +$	N₂O	D		2001^[79]
Pt₇ $O 0 — 3 +$	N₂O	D		2004^[80]
Pt₄ $O 0 — 3 -$	N₂O	D		2007^[81]
Pt_n $O - m$	O₂/N₂O	B	n=3—6, m=0—2	1998^[82]
A $u 2 -$ , Au₂ $O 2 -$	O₂	C		2003^[87]
Au₃(CO)_2—5	O₂	A	Theory	2011^[155]
A $u 6 -$	O₂	A		2002^[50]
AlV $O 3 +$ , AlV $O 4 +$	N₂O	D	Theory	2011^[91]
YAl $O 2 +$ , YAl $O 3 +$	N₂O	D	Theory	2013^[31]

Table 2 Experimentally studied catalytic oxidations of CO on atomic cluster catalysts

Catalyst	Oxidant	Reactor	Remark	Year
Al₂ $O 2 +$ , Al₂ $O 3 +$	N₂O	B		2008^[57]
Al₂ $O 2 — 4 -$	N₂O	B		2008^[57]
Ca⁺, CaO⁺	N₂O	A		2005^[41]
Ti₂ $O 3 +$ , Ti₂ $O 4 +$	N₂O	B	Theory	2011^[59]
VO₂, VO₃	N₂O	A	Theory	2013^[34]
Mn₂O₄, Mn₂O₅	NO₂	A	Theory	2013^[38]
Fe⁺, FeO⁺	N₂O	D		1981^[60]
Fe⁺, FeO⁺	N₂O	A	Theory	2005^[41]
Ge⁺, GeO⁺	N₂O	A		2005^[41]
Sr⁺, SrO⁺	N₂O	A		2005^[41]
Zr_n $O + 2 n - 1$ , Zr_n $O 2 n +$	N₂O	B	n=1—4, theory	2008^[68]
Rh_nO_m	N₂O	A	n=10—28, m=0—5	2011^[35]
Pd₆ $O 3 — 5 +$	O₂	C	Theory	2012^[25]
A $g n -$ , Ag_n $O 4 -$	O₂	C	n=7, 9, 11	2004^[74]
Ba⁺, BaO⁺	N₂O	A		2005^[41]
Eu⁺, EuO⁺	N₂O	A		2005^[41]
Yb⁺, YbO⁺	N₂O	A		2005^[41]
Os $O 0 — 4 +$	N₂O	A		2005^[41]
Ir $O 0 — 3 +$	N₂O	A		2005^[41]
Pt $O 0 — 3 +$	N₂O	A		2005^[41]
Pt⁺, Pt $O 2 +$	N₂O	D		2001^[79]
Pt₇ $O 0 — 3 +$	N₂O	D		2004^[80]
Pt₄ $O 0 — 3 -$	N₂O	D		2007^[81]
Pt_n $O - m$	O₂/N₂O	B	n=3—6, m=0—2	1998^[82]
A $u 2 -$ , Au₂ $O 2 -$	O₂	C		2003^[87]
Au₃(CO)_2—5	O₂	A	Theory	2011^[155]
A $u 6 -$	O₂	A		2002^[50]
AlV $O 3 +$ , AlV $O 4 +$	N₂O	D	Theory	2011^[91]
YAl $O 2 +$ , YAl $O 3 +$	N₂O	D	Theory	2013^[31]

Fig.15 Proposed catalytic reaction cycle on the basis of experimental and computational studies[25]

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