双金属氢氧化物催化析氧反应的协同机制研究

doi:10.6023/A20090435

摘要/Abstract

双金属氢氧化物(LDH)是催化析氧反应(OER)活性最佳的一类催化剂, 其中揭示双金属位点的协同作用是进一步提升其电催化、光催化性能的关键. 本工作采用密度泛函方法, 从理论计算角度探究了五种MN³⁺-LDH (M²⁺= Co²⁺、Ni²⁺, N³⁺=Al³⁺、Cr³⁺、Mn³⁺、Fe³⁺)在催化OER中的反应机制和双金属位点的协同作用. 研究结果表明, 在电催化OER中, 氧物种以桥连的方式同时吸附在双金属位点上, 双位点协同作用降低了OER中的电势决定步骤的自由能变, 并有效降低了电催化OER的过电位. Ni₃Fe-LDH在五种LDH中具有最高的电催化OER活性. 在光催化OER中, 双金属协同作用影响了LDH的带隙、功函数及驱动力, 进而决定了LDH光催化OER的能力. 所研究的五种LDH均为可见光响应, 其中Ni₃Cr-LDH由于其驱动力大于过电位而被预测为良好的OER光催化剂.

关键词: 双金属氢氧化物, 析氧反应, 协同作用, 催化机制, 理论计算

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

引用此文

王思, 马嘉苓, 陈利芳, 张欣. 双金属氢氧化物催化析氧反应的协同机制研究[J]. 化学学报, 2021, 79(2): 216-222.

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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图/表 9

图1. Co3Fe-LDH的原胞结构. (a)正视图, (b)俯视图

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

图2. Co3Fe-LDH (100)晶面上的CoFe桥位位点与(a) *OH, (b) *O和(c) *OOH自由基的吸附结构. (a1~c1) 正视图; (a2~c2) 俯视图. 图中绿色圆圈标注的是吸附的自由基的位置, 黑色的数字代表优化后的键长, 红色的数字代表自由基吸附于CoFe桥位位点的吸附能

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

图3. 五种LDH(100)晶面上双金属桥位位点催化OER的自由能变阶梯图

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

图4. 五种LDH的自由能与过电位(η)关系图

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)

表1. Co3Mn-LDH、Co3Fe-LDH、Ni3Fe-LDH吸附*O、*OH、*OOH的电荷分析. 括号中的数字为该位点净(100)表面与吸附物种之间的电荷转移量

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

表2. 五种LDH的光催化性能数据

Table 2. Photocatalytic performance data of five LDHs

图5. 五种LDH的态密度图

Figure 5. The projected density of states of five LDHs

图6. 五种LDH的能带边缘位置. 红色虚线为氧气的氧化电位与氢气的还原电位

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

表3. 五种LDH光生载流子的有效质量

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

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