Ethanol production from syngas over RhnNin/TiO2(n = 1, 2, 3, 4) catalysts: probing into the roles of RhnNin alloy clusters size in tuning catalytic performance
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摘要: 为明确RhnNin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RhnNin/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。
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关键词:
- 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 RhnNin/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 RhnNin 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. -
表 1 RhnNin(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 RhnNin(n = 1, 2, 3, 4) alloy clusters
Cluster Structure EB/(kJ·mol−1) Cluster Structure EB/(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 表 2 TiO2载体与RhnNin(n = 1、2、3、4)团簇之间的结合能Eb(n)和平均原子结合能$\overline E_{\mathrm{b}} $(n)
Table 2 Binding energy Eb(n) between TiO2 support and RhnNin(n = 1, 2, 3, 4) cluster and average atomic binding energy $\overline E_{\mathrm{b}} $ (n)
Catalyst E/(kJ·mol−1) Eb(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 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(Ea)及从反应物到过渡态上的C−H键缩短量(ΔDC−H)
Table 3 The activation energy (Ea) 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 (ΔDC−H) from reactant to transition state
Catalyst Rh1Ni1/TiO2 Rh2Ni2/TiO2 Rh3Ni3/TiO2 Rh4Ni4/TiO2 Ea/(kJ·mol−1) 80.0 101.0 65.3 88.2 △DC−H/Å 1.386 1.886 1.082 1.627 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(Ga 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 (Ga 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 Ga ΔG f/i Ga 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 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 θCO 5.44×10−2 1.39×10−5 θH 2.23×10−5 1.29×10−8 θCHO 1.19×10−8 1.00 θCH 3.15×10−6 1.53×10−21 θCHOH 5.18×10−13 8.46×10−11 $\theta_{{\mathrm{CH_2 OH}}} $ 4.24×10−2 2.09×10−4 θCHCHO 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% 表 6 RhnNin/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 RhnNin/TiO2(n = 1, 2, 3, 4)
Catalyst △qRh/e △qNi/e △qTi/e △qO/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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