Role of Synergistic Effect in Oxygen Evolution Reaction over Layered Double Hydroxide

doi:10.6023/A20090435

Abstract

Layered double hydroxides (LDHs) has played an important role in the field of catalysis because of its high dispersion of active sites, adjustable layer elements, and exchangeable interlayer anions. LDHs show excellent catalytic activity in oxygen evolution reaction (OER), due to the specific synergistic effect of double metals site. Thus, it is crucial to reveal the role of synergistic effect for promoting catalytic performance of photocatalyst and electrocatalyst. Although great efforts from experimental workers have been devoted to exploring the types and ratios of bimetals in LDHs, the role of synergistic effect on OER is still unclear. In this work, we systematically investigated the synergistic mechanism and the role of synergistic effect on OER performances based on density functional theory calculation plus U (DFT+U) method. Five kinds of LDHs (MN³⁺-LDH (M²⁺=Co²⁺, Ni²⁺; N³⁺=Al³⁺, Cr³⁺, Mn³⁺, Fe³⁺)) were built to study the synergistic effect from different bimetal. The results showed that oxygen species is bridged by one M²⁺and one N³⁺metal, forming a stable adsorption structure. For electrocatalytic OER, the synergistic effect of the bimetallic sites decreased the free energy change of the potential-determining step, and further reduces the overpotential of the electrocatalytic oxygen evolution reaction. Therein, Ni₃Fe-LDH has the lowest overpotential, exhibiting superior electrocatalytic OER activity among the five LDHs. This is not the case in photocatalytic OER, the synergy of bimetals affects the band gap, work function and driving force of LDHs, which determine the ability of LDH photocatalytic OER. The five types of LDH studied are all visible light response, and Ni₃Cr-LDH is predicted to be a good OER photocatalyst in view of its higher driving force than the overpotential. This work reveals the synergistic effect of bimetal in LDH on OER activity from a micro-atomic level, which will provide theoretical insights for the design of novel LDH-based catalysts.

Key words: layered double hydroxide, oxygen evolution reaction, synergy, catalytic mechanism, theoretical calculation

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Si Wang, Jialing Ma, Lifang Chen, Xin Zhang. Role of Synergistic Effect in Oxygen Evolution Reaction over Layered Double Hydroxide[J]. Acta Chimica Sinica, 2021, 79(2): 216-222.

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Fig. & Tab. 9

Figure 1. Cell structure of Co3Fe-LDH. (a) Front view, (b) top view

Figure 2. Optimized structures of (a) *OH, (b) *O and (c) *OOH radicals adsorbed at CoFe bridge site of Co 3Fe-LDH (100) faces. (a1~c1) Front view; (a2~c2) top view. The green circle in the figure indicates the position of the adsorbed free radical, the black number represents the optimized bond length, and the red number represents the binding energy of the free radical adsorbed at the CoFe bridge site

Figure 3. Ladder diagram of ΔG of the four-step elementary reaction at double metal bridging sites of five LDHs (100) surface

Figure 4. The relationship between free energy and overpotentials of five LDHs

双金属氢氧化物	原子	(100)晶面	(100)-O	(100)-OH	(100)-OOH
Co₃Mn-LDH	Co	0.47	0.75(0.28)	0.70(0.23)	0.69(0.22)
Co₃Mn-LDH	Mn	0.64	0.90(0.26)	0.92(0.28)	0.83(0.19)
Co₃Fe-LDH	Co	0.49	0.78(0.29)	0.71(0.22)	0.69(0.20)
Co₃Fe-LDH	Fe	0.61	0.90(0.29)	0.84(0.23)	0.85(0.24)
Ni₃Fe-LDH	Ni	0.53	0.72(0.19)	0.64(0.11)	0.68(0.15)
Ni₃Fe-LDH	Fe	0.67	1.04(0.37)	0.97(0.30)	0.94(0.27)

Table 1. Charge analysis of *O, *OH and *OOH adsorbed on Co3Mn-LDH, Co3Fe-LDH and Ni3Fe-LDH, respectively. The number in parentheses is magnitude of the charge transfer between (100) surface and adsorption species

双金属氢氧化物	E_g/eV	k-vector of VBM	k-vector of CBM	W/eV	E_VBM/eV
Ni₃Cr-LDH	1.943	0.893	0.286	4.834	–5.805	–3.862	0.485
Ni₃Al-LDH	2.525	0.000	0.892	4.162	–5.424	–2.899	0.104
Co₃Mn-LDH	1.705	0.785	0.000	3.922	–4.774	–3.069	–0.545
Co₃Fe-LDH	1.554	1.000	0.214	3.924	–4.701	–3.147	–0.619
Ni₃Fe-LDH	1.214	0.892	0.000	3.674	4.281	–3.067	–1.039

Table 2. Photocatalytic performance data of five LDHs

Figure 5. The projected density of states of five LDHs

Figure 6. Band edge placements of the five LDHs. The red dashed lines in the figure represent the oxidation potential of oxygen and the reduction potential of hydrogen

LDH	有效质量
LDH	m_e*/m₀	m_h*/m₀
Co₃Fe-LDH	6.01	3.62
Ni₃Cr-LDH	2.61	8.22
Ni₃Al-LDH	20.55	14.17
Ni₃Fe-LDH	46.48	79.21
Co₃Mn-LDH	7.96	4.98

Table 3. The effective mass of electrons and holes of the five LDHs

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双金属氢氧化物催化析氧反应的协同机制研究