RhnNin/TiO2(n = 1、2、3、4)催化剂中RhnNin合金团簇尺寸调控合成气制乙醇反应性能

张静静; 凌丽霞; 马彩萍; 章日光; 王宝俊

doi:10.1016/S1872-5813(24)60454-8

Rh_nNi_n/TiO₂(n = 1、2、3、4)催化剂中Rh_nNi_n合金团簇尺寸调控合成气制乙醇反应性能

doi: 10.1016/S1872-5813(24)60454-8

张静静^1,,
凌丽霞^1, ,,
马彩萍^1,,
章日光^2,,
王宝俊^{1, 2,}

1.
太原理工大学化学工程与技术学院, 山西太原 030024
2.
太原理工大学省部共建煤基能源清洁高效利用国家重点实验室, 山西太原 030024

基金项目: 国家重点研发计划(2021YFA1502804)，国家自然科学基金(21736007)和山西浙大新材料与化工研究院研发项目(2022SX-FR001)资助

详细信息

通讯作者:
Tel:13834531385, E-mail: linglixia@tyut.edu.cn

中图分类号: O643.32
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出版历程
- 收稿日期: 2024-03-12
- 修回日期: 2024-04-17
- 录用日期: 2024-04-20
- 网络出版日期: 2024-05-21

Ethanol production from syngas over Rh_nNi_n/TiO₂(n = 1, 2, 3, 4) catalysts: probing into the roles of Rh_nNi_n alloy clusters size in tuning catalytic performance

ZHANG Jingjing^1
,,
LING Lixia^{1
, ,},
MA Caiping^1
,,
ZHANG Riguang^2
,,
WANG Baojun^{1, 2
,}

1.
College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
2.
State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China

Funds: The project was supported by National Key R&D Program of China (2021YFA1502804), the Key Program of National Natural Science Foundation of China (21736007), and the supported by Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering (2022SX-FR001).

摘要

摘要: 为明确Rh_nNi_n合金团簇尺寸诱导的金属-载体相互作用对合成气制乙醇反应性能的调控机制，本工作采用密度泛函理论（DFT）和微观动力学方法研究了不同Rh-Ni合金团簇尺寸Rh_nNi_n/TiO₂(n = 1、2、3、4)上合成气制乙醇反应。结果表明，Rh₁Ni₁/TiO₂和Rh₃Ni₃/TiO₂能够显著促进CO活化转化及C−C链的形成，并抑制甲烷的生成。其中，Rh₁Ni₁/TiO₂表现出最高的乙醇生成活性和相对选择性。电子性质分析表明，在Rh₁Ni₁/TiO₂催化剂上，合金团簇上Ni原子及载体上Ti和O原子向Rh原子转移的电荷最多，合金团簇上Rh-Ni间相互作用最强，且合金团簇与TiO₂载体间的相互作用最强，催化剂的催化活性最高。在525 K下，从头算分子动力学模拟（AIMD）模拟显示Rh₁Ni₁/TiO₂催化剂具有较高的热稳定性。
- 合成气制乙醇 /
- Rh-Ni合金团簇尺寸 /
- 金属-载体间相互作用 /
- 密度泛函理论
Abstract: The direct production of ethanol from syngas on Rh_nNi_n/TiO₂ (n = 1, 2, 3, 4) has been investigated by using density functional theory (DFT) and micro-kinetic methods, in order to elucidate the regulatory mechanism of Rh_nNi_n alloy cluster size-induced metal-support interactions on the performance of ethanol synthesis. The results showed that Rh₁Ni₁/TiO₂ and Rh₃Ni₃/TiO₂ can significantly enhance the CO conversion and C−C chain formation, while inhibiting the methane generation. Among them, Rh₁Ni₁/TiO₂ exhibits the highest ethanol generation activity and relative selectivity. Electronic property analyses revealed that Ni atoms on the alloy clusters and Ti and O atoms on the supports transferred the most of charge to the Rh atoms on the Rh₁Ni₁/TiO₂ catalysts. The Rh-Ni interactions on the alloy clusters were the strongest, and the alloy clusters exhibited the strongest interactions with the TiO₂ supports, resulting in the highest catalytic activity among the catalysts. Ab-initio molecular dynamics (AIMD) simulations at 525 K showed that the Rh₁Ni₁/TiO₂ catalyst exhibited high thermal stability.
- ethanol production from syngas /
- Rh-Ni alloy cluster size /
- metal-support interaction /
- density functional theory

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图 1 Rh_nNi_n/TiO₂（n = 1、2、3、4）模型最稳定结构的俯视图和侧视图

Figure 1 Top and side views of the optimized structures of Rh_nNi_n/TiO₂(n = 1, 2, 3, 4) models

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图 2 525 K下（1） Rh₁Ni₁/TiO₂、（2） Rh₂Ni₂/TiO₂、（3） Rh₃Ni₃/TiO₂和（4） Rh₄Ni₄/TiO₂催化剂上CO活化反应的势能图及始态、过渡态及终态结构

Figure 2 Activation free energy diagrams and corresponding structures of the CO activation of (1) Rh₁Ni₁/TiO₂, (2) Rh₂Ni₂/TiO₂, (3) Rh₃Ni₃/TiO₂ and (4) Rh₄Ni₄/TiO₂ at 525 K

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图 3 525 K下Rh_nNi_n/TiO₂（n = 1、2、3、4）催化剂上CO活化、甲烷生成、C−C链形成及乙醇生成反应所需的活化自由能

Figure 3 Activation free energy required for CO activation, methane formation, C−C chain and ethanol formation on Rh_nNi_n/TiO₂(n = 1, 2, 3, 4) at 525 K

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图 4 525 下Rh₁Ni₁/TiO₂及Rh₃Ni₃/TiO₂催化剂上CH生成反应的势能及始态、过渡态及终态结构

Figure 4 Activation free energy diagrams corresponding to CH production from syngas on the surfaces of Rh₁Ni₁/TiO₂ and Rh₃Ni₃/TiO₂ at 525 K and structure diagram of initial, transition and final states of reaction

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图 5 525 K下Rh₁Ni₁/TiO₂及Rh₃Ni₃/TiO₂催化剂上CH₂生成反应的势能及始态、过渡态及终态结构

Figure 5 Activation free energy diagram corresponding to CH₂ production from syngas on the surfaces of Rh₁Ni₁/TiO₂ and Rh₃Ni₃/TiO₂ at 525 K and structure diagram of initial, transition and final states of reaction

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图 6 525 K下Rh₁Ni₁/TiO₂及Rh₃Ni₃/TiO₂催化剂上CH₃生成反应的势能及始态、过渡态及终态结构

Figure 6 Activation free energy diagram corresponding to CH₃ production from syngas on the surfaces of Rh₁Ni₁/TiO₂ and Rh₃Ni₃/TiO₂ at 525 K and structure diagram of initial, transition and final states of reaction

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图 7 525 K下Rh₁Ni₁/TiO₂及Rh₃Ni₃/TiO₂催化剂上CH₃OH生成反应的势能

Figure 7 Activation free energy diagram corresponding to CH₃OH production from syngas on the surfaces of Rh₁Ni₁/TiO₂ and Rh₃Ni₃/TiO₂ at 525 K

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图 8 525 K下Rh（111）、Rh₁Ni₁/TiO₂和Rh₃Ni₃/TiO₂催化剂上CH_x和CH₃OH生成反应的总能垒（[a]指参考文献9）

Figure 8 Overall activation energy diagram of CH_x and methanol formation on the surfaces of Rh(111), Rh₁Ni₁/TiO₂ and Rh₃Ni₃/TiO₂ at 525 K ([a] refers to reference 9)

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图 9 525 K下Rh₁Ni₁/TiO₂上C−C链形成相关反应势能及始态、过渡态及终态结构

Figure 9 Activation free energy diagram of C−C chain formation related reactions on the surface of Rh₁Ni₁/TiO₂ at 525 K and structure diagram of initial, transition and final states of reaction

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图 10 525 K下Rh₃Ni₃/TiO₂上C–C链形成相关反应的势能及始态、过渡态及终态结构

Figure 10 Activation free energy diagram of C–C chain formation related reactions on the surface of Rh₃Ni₃/TiO₂ at 525 K and structure diagram of initial, transition and final states of reaction

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图 11 525 K下Rh₁Ni₁/TiO₂和Rh₃Ni₃/TiO₂催化剂上CH₃CH₂OH生成反应的势能及始态、过渡态及终态结构

Figure 11 Activation free energy diagram of ethanol formation from syngas on the surfaces of Rh₁Ni₁/TiO₂ and Rh₃Ni₃/TiO₂ at 525 K and structure diagram of initial, transition and final states of reaction

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图 12 Rh_nNi_n/TiO₂（n = 1、2、3、4）表面电荷差分密度

Figure 12 Differential charge density of Rh_nNi_n/TiO₂(n = 1, 2, 3, 4) surface

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图 13 Rh₁Ni₁/TiO₂催化剂AIMD模拟总能量和温度随时间的变化及催化剂最终稳定构型的俯视图和侧视图

Figure 13 Variation of the total energy and temperature against time for the AIMD simulation of Rh₁Ni₁/TiO₂. The insets are the top and side views of the snapshot of the final configuration

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表 1 Rh_nNi_n（n = 1、2、3、4）合金团簇同分异构体构型及结合能

Table 1 Configuration and binding energy of isomers of Rh_nNi_n(n = 1, 2, 3, 4) alloy clusters

Cluster	Structure	E_B/（kJ·mol⁻¹）	Cluster	Structure	E_B/（kJ·mol⁻¹）
Rh₁Ni₁		157.4	Rh₄Ni₄-1		328.5
Rh₂Ni₂		251.2	Rh₄Ni₄-2		329.4
Rh₃Ni₃-1		301.7	Rh₄Ni₄-3		328.0
Rh₃Ni₃-2		300.2	Rh₄Ni₄-4		326.9
			Rh₄Ni₄-5		327.1

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表 2 TiO₂载体与Rh_nNi_n（n = 1、2、3、4）团簇之间的结合能E_b（n）和平均原子结合能$\overline E_{\mathrm{b}} $（n）

Table 2 Binding energy E_b(n) between TiO₂ support and Rh_nNi_n(n = 1, 2, 3, 4) cluster and average atomic binding energy $\overline E_{\mathrm{b}} $ (n)

Catalyst	E/(kJ·mol⁻¹)
Catalyst	E_b(n)	$\overline E_{\mathrm{b}} $(n)
Rh₁Ni₁/TiO₂	−368.7	−184.3
Rh₂Ni₂/TiO₂	−531.1	−132.8
Rh₃Ni₃/TiO₂	−346.5	−57.7
Rh₄Ni₄/TiO₂	−449.9	−56.2

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表 3 由CO活化生成CHO过程中（1） Rh₁Ni₁/TiO₂、（2） Rh₂Ni₂/TiO₂、（3） Rh₃Ni₃/TiO₂和（4） Rh₄Ni₄/TiO₂催化剂上C−H键形成的活化能（E_a）及从反应物到过渡态上的C−H键缩短量（ΔD_C−H）

Table 3 The activation energy (E_a) for C−H bond formation on (1) Rh₁Ni₁/TiO₂、(2) Rh₂Ni₂/TiO₂、(3) Rh₃Ni₃/TiO₂ and (4) Rh₄Ni₄/TiO₂ catalysts during CHO formation from CO activation and the C−H bond shortening (ΔD_C−H) from reactant to transition state

Catalyst	Rh₁Ni₁/TiO₂	Rh₂Ni₂/TiO₂	Rh₃Ni₃/TiO₂	Rh₄Ni₄/TiO₂
E_a/(kJ·mol⁻¹)	80.0	101.0	65.3	88.2
△D_C−H/Å	1.386	1.886	1.082	1.627

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表 4 525K下Rh₁Ni₁/TiO₂和Rh₃Ni₃/TiO₂催化剂表面上乙醇生成中所涉及基元反应的活化自由能（G_a kJ/mol）、反应自由热（ΔG kJ/mol）及基元反应对应的唯一虚频

Table 4 Activation free energies (G_a kJ/mol), reaction free energies (ΔG kJ/mol) and the unique imaginary frequency of the elementary reactions involved in the formation of C₂H₅OH over Rh₁Ni₁/TiO₂ and Rh₃Ni₃/TiO₂ catalysts at 525 K

Elementary step		Rh₁Ni₁/TiO₂			Rh₃Ni₃/TiO₂
Elementary step		G_a	ΔG	f/i	G_a	ΔG	f/i
R-1	CO→C+O	267.7	142.5	95.9i	300.0	147.5	299.8i
R-2	CO+H→COH	118.8	26.7	1502.2i	139.2	61.9	1468.2i
R-3	CO+H→CHO	80.0	55.0	243.6i	65.3	61.7	214.8i
R-4	CHO+H→CHOH	62.5	8.0	500.3i	114.1	49.0	861.6i
R-5	CHOH→CH+OH	26.0	−50.9	186.9i	30.9	−88.1	312.9i
R-6	CHO+H→CH+OH	16.0	−69.3	329.5i	133.8	−39.1	299.0i
R-7	CHO→CH+O	21.3	−58.7	370.8i	215.6	124.7	181.4i
R-8	CHO+H→CH₂O	54.8	7.3	735.7i	116.2	89.8	750.2i
R-9	CH₂O→CH₂+O	87.6	−48.4	191.2i	90.3	−29.7	166.8i
R-10	CH₂O+H→CH₂+OH	192.5	51.9	127.0i	157.1	28.8	391.7i
R-11	CH₂O+H→CH₂OH	75.5	−18.5	952.9i	129.4	93.9	1041.8i
R-12	CHOH+H→CH₂OH	18.7	−24.9	383.3i	12.9	−18.4	669.0i
R-13	CH₂OH→CH₂+OH	78.7	17.2	254.2i	103.9	−5.3	157.2i
R-14	CH₂O+H→CH₃O	107.5	−17.2	668.0i	107.6	39.1	625.4i
R-15	CH₃O→CH₃+O	79.0	−135.7	552.3i	140.2	−29.2	125.0i
R-16	CH₃O+H→CH₃+OH	162.2	47.0	971.0i	160.9	−144.9	570.4i
R-17	CH₃O+H→CH₃OH	129.1	89.1	901.1i	68.3	7.3	1038.9i
R-18	CH₂OH+H→CH₃OH	128.3	88.0	368.1i	77.1	37.3	710.4i
R-19	CH+H→CH₂	107.3	19.1	617.7i	38.0	26.7	496.3i
R-20	CH₂+H→CH₃	70.7	14.5	692.0i	62.9	32.3	722.7i
R-21	CH₃+H→CH₄	149.7	71.0	1189.9i	37.9	0.0	781.4i
R-22	CH+CH→C₂H₂	41.0	−65.9	343.9i	113.0	81.9	64.5i
R-23	CH+CO→CHCO	16.3	−18.0	119.0i	213.5	127.5	405.5i
R-24	CH+CHO→CHCHO	7.5	−53.8	175.6i	50.1	−122.5	219.2i
R-25	CHO+CHO→C₂H₂O₂	33.8	−91.4	329.3i	88.2	52.8	477.9i
R-26	C₂H₂O₂→CHCHO+O	141.6	−78.7	93.1i	219.2	18.2	421.9i
R-27	CHCO+H→CH₂CO	51.3	19.7	672.7i	63.5	−40.9	830.6i
R-28	CHCO+H→CHCHO	77.9	15.7	168.8i	129.6	−22.7	214.2i
R-29	CHCO+H→CHCOH	154.0	66.1	1382.0i	132.3	−14.8	566.4i
R-30	CH₂+CH₂→C₂H₄	—	—	—	89.8	−67.7	70.9 i
R-31	CH₂+CO→CH₂CO	—	—	—	84.3	11.0	302.7i
R-32	CH₂+CHO→CH₂CHO	—	—	—	148.0	23.1	168.9i
R-33	CH₃+CH₃→C₂H₆	—	—	—	209.6	75.3	542.8i
R-34	CH₃+CO→CH₃CO	—	—	—	87.0	50.1	497.2i
R-35	CH₃+CHO→CH₃CHO	—	—	—	65.1	9.3	138.3i
R-36	CHCHO+H→CH₂CHO	23.8	2.7	417.2i	30.6	−1.4	647.5i
R-37	CHCHO+H→CHCHOH	257.9	48.0	895.6i	86.9	29.9	1107.7i
R-38	CH₂CHO+H→CH₃CHO	63.0	33.5	337.4i	18.8	−15.2	269.3i
R-39	CH₂CO+H→CH₂CHO	75.4	21.2	311.6i	—	—	—
R-40	CH₂CO+H→CH₂COH	143.9	57.8	971.5i	—	—	—
R-41	CH₂CHO+H→CH₂CHOH	107.7	3.0	786.4i	104.8	60.9	1069.5i
R-42	CH₃CHO+H→CH₃CH₂O	50.6	−17.7	395.1i	54.9	−25.9	489.0i
R-43	CH₃CHO+H→CH₃CHOH	164.3	108.5	516.3i	132.0	106.3	1089.7i
R-44	CH₃CH₂O+H→C₂H₅OH	95.0	76.7	424.2i	44.4	−17.0	1147.5i

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表 5 525 K下Rh₁Ni₁/TiO₂和Rh₃Ni₃/TiO₂催化剂上乙醇生成有利路径中涉及中间体覆盖度及产物形成速率

Table 5 Intermediate coverage and product formation rates involved in favorable pathways for the formation of ethanol on Rh₁Ni₁/TiO₂ and Rh₃Ni₃/TiO₂ catalysts at 525 K

Parameter		Rh₁Ni₁/TiO₂	Rh₃Ni₃/TiO₂
Coverage	θ_CO	5.44×10⁻²	1.39×10⁻⁵
	θ_H	2.23×10⁻⁵	1.29×10⁻⁸
	θ_CHO	1.19×10⁻⁸	1.00
	θ_CH	3.15×10⁻⁶	1.53×10⁻²¹
	θ_CHOH	5.18×10⁻¹³	8.46×10⁻¹¹
	$\theta_{{\mathrm{CH_2 OH}}} $	4.24×10⁻²	2.09×10⁻⁴
	θ_CHCHO	6.94×10⁻⁸	1.38×10⁻¹⁵
	$\theta_{{\mathrm{CH_2CHO}}} $	5.54×10⁻⁴	9.27×10⁻¹⁷
	$\theta_{{\mathrm{CH_3CHO}}} $	3.27×10⁻⁵	3.63×10⁻¹³
	$\theta_{{\mathrm{CH_3CH_2O}}} $	8.51×10⁻¹	3.26×10⁻¹⁴
	$\theta_{{\mathrm{CH_2}}} $	7.21×10⁻¹⁰	4.55×10⁻¹⁹
	$\theta_{{\mathrm{CH_3}}} $	5.13×10⁻²	1.48×10⁻²¹
	θ_*	4.73×10⁻¹⁰	2.22×10⁻¹³
Formation rate/s⁻¹	$r_{{\mathrm{CH_3OH}}} $	1.76×10⁻⁶	6.21×10⁻⁷
	$r_{{\mathrm{CH_4}}} $	1.62×10⁻⁸	3.53×10⁻²⁰
	$r_{{\mathrm{C_2H_2}}} $	9.11×10⁻³	1.47×10⁻⁴⁰
	$r_{{\mathrm{C_2H_5OH}}} $	7.35×10⁻²	1.75×10⁻¹³
Relative selectivity/%	$s_{{\mathrm{CH_3OH}}} $	0.00%	100.00%
	$s_{{\mathrm{CH_4}}} $	0.00%	0.00%
	$s_{{\mathrm{C_2H_2}}} $	11.03%	0.00%
	$s_{{\mathrm{C_2H_5OH}}} $	88.97%	0.00%

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表 6 Rh_nNi_n/TiO₂（n = 1、2、3、4）上Ni、Ti及O原子平均失去电荷量及Rh原子平均得到电荷量

Table 6 The amount of average charge loss of Ni, Ti and O atoms and average amount in charge gain of Rh atoms over Rh_nNi_n/TiO₂(n = 1, 2, 3, 4)

Catalyst	△q_Rh/e	△q_Ni/e	△q_Ti/e	△q_O/e
Rh₁Ni₁/TiO₂	0.627	−0.389	−2.268	−0.801
Rh₂Ni₂/TiO₂	0.198	−0.232	−2.188	−0.805
Rh₃Ni₃/TiO₂	0.064	−0.132	−2.169	−0.805
Rh₄Ni₄/TiO₂	0.088	−0.039	−2.224	−0.795

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