催化学报 ›› 2022, Vol. 43 ›› Issue (6): 1417-1432.DOI: 10.1016/S1872-2067(21)63980-3
吕奉磊a,b,c,†, 花伟a,b,c,†, 邬慧蓉a,b,c, 孙浩a,b,c, 邓昭a,b,c, 彭扬a,b,c,*()
收稿日期:
2021-09-16
接受日期:
2021-09-16
出版日期:
2022-06-18
发布日期:
2022-04-14
通讯作者:
彭扬
作者简介:
第一联系人:†共同第一作者
基金资助:
Fenglei Lyua,b,c,†, Wei Huaa,b,c,†, Huirong Wua,b,c, Hao Suna,b,c, Zhao Denga,b,c, Yang Penga,b,c,*()
Received:
2021-09-16
Accepted:
2021-09-16
Online:
2022-06-18
Published:
2022-04-14
Contact:
Yang Peng
About author:
First author contact:†Contributed equally to this work.
Supported by:
摘要:
电催化二氧化碳还原(CO2RR)利用可再生能源(如太阳能和风能)将CO2转化为燃料和高附加值化学品, 因而被广泛认为是“一石二鸟”的绿色技术来解决能源与环境问题. 然而, CO2RR的大规模应用仍严重受限于缺乏高效稳定的CO2RR催化剂. 非均相分子催化剂和金属-有机框架因具有明确的结构且金属中心和配体可以调节与修饰, 在CO2RR的基础研究和实际应用中都展现出巨大潜力.
本文综述了这些具有明确结构的金属-有机配位化合物的结构与界面调控应用于CO2RR领域的工作. 介绍了CO2RR的基础电化学、催化剂的性能评价指标(包括过电位、法拉第效率、塔菲尔斜率、转化频率和电化学能量效率)和三种常用电解池(H型电解池、流动电解池和膜电极组件)的优缺点. 重点总结近期非均相分子催化剂中金属中心、配体效应和分子-载体相互作用的调控及金属-有机框架的结构工程和原位重构等方面的重点工作. 迄今, 具有不同金属中心(如Mn、Fe、Co、Ni、Cu和Zn等)和配体(包括酞菁、卟啉和金属中心轴向配位等)的非均相分子催化剂和金属-有机框架被报道用于高效CO2RR. 调节催化剂-载体相互作用, 抑制催化剂团聚并增强其导电性, 可有效地提高分子催化剂的活性和稳定性. 制备导电金属-有机框架、在金属-有机框架中引入活性位点或促进剂并控制金属-有机框架的原位重构, 为构建高效CO2RR催化剂带来更多机会.
金属-有机配位化合物的结构和界面工程是发展高效CO2RR催化剂的重要方向. 然而, 金属-有机配位化合物用于CO2RR仍处于初级发展阶段, 充分发挥其潜力任重道远. 根据目前研究面临的问题, 总结和展望该领域未来应关注的方向: (1)定向合成新颖分子催化剂、金属-有机框架和载体及其结构和界面的精准调控; (2)非均相分子催化剂和金属-有机框架在CO2RR的大规模应用; (3)追踪和调控非均相分子催化剂和金属-有机框架的重构; (4)阐明金属-有机配位结构和CO2RR性能的构-效关系. 本文为高效CO2RR催化剂设计与合成提供一定参考.
吕奉磊, 花伟, 邬慧蓉, 孙浩, 邓昭, 彭扬. 金属-有机配位结构与界面调控电催化二氧化碳还原[J]. 催化学报, 2022, 43(6): 1417-1432.
Fenglei Lyu, Wei Hua, Huirong Wu, Hao Sun, Zhao Deng, Yang Peng. Structural and interfacial engineering of well-defined metal-organic ensembles for electrocatalytic carbon dioxide reduction[J]. Chinese Journal of Catalysis, 2022, 43(6): 1417-1432.
Equation | E0 vs. NHE at pH = 7 | Electron transfer number |
---|---|---|
CO2 + e- → CO2•- | -1.90 | 1 |
CO2 + 2e-+ 2H+ → CO + H2O | -0.53 | 2 |
CO2 + 2e- + 2H+ → HCOOH | -0.61 | 2 |
CO2 + 6e- + 6H+ → CH3OH + H2O | -0.38 | 6 |
CO2 + 8e- + 8H+ → CH4 + 2H2O | -0.24 | 8 |
2CO2 + 12e- + 12H+ → C2H4 + 4H2O 2CO2 + 12e- + 12H+ → C2H5OH + 3H2O 2H+ + 2e- → H2 | -0.34 -0.33 -0.42 | 12 12 2 |
Table 1 Standard potentials for CO2RR and hydrogen evolution reaction [33,34].
Equation | E0 vs. NHE at pH = 7 | Electron transfer number |
---|---|---|
CO2 + e- → CO2•- | -1.90 | 1 |
CO2 + 2e-+ 2H+ → CO + H2O | -0.53 | 2 |
CO2 + 2e- + 2H+ → HCOOH | -0.61 | 2 |
CO2 + 6e- + 6H+ → CH3OH + H2O | -0.38 | 6 |
CO2 + 8e- + 8H+ → CH4 + 2H2O | -0.24 | 8 |
2CO2 + 12e- + 12H+ → C2H4 + 4H2O 2CO2 + 12e- + 12H+ → C2H5OH + 3H2O 2H+ + 2e- → H2 | -0.34 -0.33 -0.42 | 12 12 2 |
Fig. 2. Molecular structure of PorCu (a), Faradaic efficiencies (b) and partial current densities (c) for the gas-phase products at -0.976 V vs. RHE. (a?c) Reprinted with permission from Ref. [42]. Copyright 2016, American Chemical Society. (d) Chemical structures of the PorZn and H2Por, (e) CO Faradaic efficiencies and CO partial current densities at different potentials and (f) CO Faradaic efficiencies and total current densities after electrolysis at -1.7 V vs. standard hydrogen electrode (SHE). (d?f) Reprinted with permission from Ref. [43]. Copyright 2017, American Chemical Society. (g) Calculated free-energy diagram for all the MePc electrodes, (h) LSV tests in CO2-saturated 0.5 mol/L KHCO3 and (i) CO current density of MePcs at various potentials. (g?i) Reprinted with permission from Ref. [44]. Copyright 2018, Wiley-VCH.
Fig. 3. Molecular structures of CoPc1 (a) and CoPc2 (b). (c) Current density and TOF for CoPc1@MWCNTs and CoPc2@MWCNTs for CO production in CO2-saturated 0.5 mol/L KHCO3. (a?c) Reprinted with permission from Ref. [48]. Copyright 2019, the Springer-Nature. (d) Molecular structures of NiPc, NiPc-OMe and NiPc-CN. (e) Linear sweep voltammetry of neat NiPc, P-NiNC, NiPc MDE, NiPc-OMe MDE and NiPc-CN MDE in CO2-saturated 0.5 mol/L KHCO3 at scan rate of 5 mV s-1. (f) Chronoamperometry of NiPc MDE at -0.68 V, NiPc-CN MDE at -0.56 V and NiPc-OMe MDE at -0.64 V. (d?f) Reprinted with permission from Ref. [49]. Copyright 2020, the Springer-Nature. (g) Molecular structures of CoPc-A; Total current density (h) and Faradic efficiencies (i) for CO and H2 of CCG/CoPc-A and CCG/CoPc hybrids in CO2-saturated 0.1 mol/L KHCO3. (g?i) Reprinted with permission from Ref. [51]. Copyright 2019 American Chemical Society.
Fig. 4. Molecular structure comparison of Co-porphine (a) and Co(II)CPY (b). LSV curves (c) and FE (d) of CO for Co(II)CPY/CNT and CoTPP/CNT in CO2-saturated 0.1 mol/L KHCO3 at a scan rate of 1 mV s-1. (a?d) Reprinted with permission from Ref. [54]. Copyright 2020, Wiley-VCH. (e) Molecular structure of Co-salophen-X. FECO (f) and jCO (g) at selected potentials over the three Co-salophen-X samples. (e?g) Reprinted with permission from Ref. [40]. Copyright 2021 Elsevier. Molecular structure of Ni-N4-TPP (h) and Ni(-Cl)-N3O-TPP (i). FETotal and FECO (j) and jTotal and jCO (k) acquired for 1 h CO2RR operation at various potentials in a H-cell. (h?k) Reprinted with permission from Ref. [55]. Copyright 2021, American Chemical Society.
Fig. 5. (a) An illustration of CoPc immobilized in P4VP. Reprinted with permission from Ref. [56]. Copyright 2016, The Royal Society of Chemistry. (b) A proposed mechanism for CO2 reduction by CoPc showing pathway for competitive H2 generation. Reprinted with permission from Ref. [57]. Copyright 2019, the Springer-Nature. Interaction between pyridine and central Co (c) and Co 3d orbital splitting of Co centers (d) in MTPyP-Co and STPyP-Co obtained from multiplet fitting of Co L-edge absorption. (c,d) Reprinted with permission from Ref. [58]. Copyright 2019, Wiley-VCH.
Fig. 6. Schematic illustrations of adsorbed CoPc molecules on GDY/G (a) and graphene (b). (c) Linear sweep voltammetry with a scan rate of 20 mV s-1. (d) FECO and FEH2 of CoPc, CoPc/G, and CoPc/GDY/G. (a?d) Reprinted with permission from Ref. [63]. Copyright 2021, American Chemical Society. (e) Schematics showing the structure of Co-Nx (x = 2-5) centers in the MOLs; Linear sweep voltammetry (f) and Faradaic efficiencies (g) of MOL-Co-N3, MOL-Co-N4, MOL-Co-N5, and MOL-Co-N2 in CO2-saturated 1.0 mol/L KHCO3. (e?g) Reprinted with permission from Ref. [64]. Copyright 2021, American Chemical Society. (h) Supramolecular structure of Fe-PB composed of six Fe-TPP monomer building blocks. Faradaic efficiencies of CO and H2 (i) and CO specific current densities (j) for Fe-PB and Fe-TPP. (h?j) Reprinted with permission from Ref. [65]. Copyright 2018, Wiley-VCH.
Catalyst | Cell | Electrolyte | j (mA cm-2) | Product FE | Stability | Ref. |
---|---|---|---|---|---|---|
PorCu | H | 0.5 mol/L KHCO3 | 49 | CH4 27%, C2H4 17% | — | [ |
CoPc | H | 0.5 mol/L KHCO3 | ~8 | CO 99% | 60h@-0.8V | [ |
NiPc-OMe | flow | 1 mol/L KHCO3 | 300 | CO 99.5% | 40h@150mA cm-2 | [ |
CoTMAPc | flow | 1 mol/L KOH | 239 | CO 95.6% | 15h@-0.4V | [ |
CoCPY | H | 0.1 mol/L KHCO3 | 10.73 | CO 96% | 11h@-0.55V | [ |
STPyP-Co | H | 0.5 mol/L KHCO3 | 6.5 | CO 96% | 48h@-0.62V | [ |
CoPc/GDY/G | H | 0.1 mol/L KHCO3 | 9 | CO 96% | 24h@-0.81V | [ |
MOL-Co-N3 | H | 1 mol/L KHCO3 | 13.3 | CO 99% | 1.5h@-0.5V | [ |
Fe-PB | H | 0.5 mol/L KHCO3 | ~1.6 | CO 100% | 24h@-0.63V | [ |
Table 2 Comparisons of different heterogeneous molecular catalysts for CO2RR.
Catalyst | Cell | Electrolyte | j (mA cm-2) | Product FE | Stability | Ref. |
---|---|---|---|---|---|---|
PorCu | H | 0.5 mol/L KHCO3 | 49 | CH4 27%, C2H4 17% | — | [ |
CoPc | H | 0.5 mol/L KHCO3 | ~8 | CO 99% | 60h@-0.8V | [ |
NiPc-OMe | flow | 1 mol/L KHCO3 | 300 | CO 99.5% | 40h@150mA cm-2 | [ |
CoTMAPc | flow | 1 mol/L KOH | 239 | CO 95.6% | 15h@-0.4V | [ |
CoCPY | H | 0.1 mol/L KHCO3 | 10.73 | CO 96% | 11h@-0.55V | [ |
STPyP-Co | H | 0.5 mol/L KHCO3 | 6.5 | CO 96% | 48h@-0.62V | [ |
CoPc/GDY/G | H | 0.1 mol/L KHCO3 | 9 | CO 96% | 24h@-0.81V | [ |
MOL-Co-N3 | H | 1 mol/L KHCO3 | 13.3 | CO 99% | 1.5h@-0.5V | [ |
Fe-PB | H | 0.5 mol/L KHCO3 | ~1.6 | CO 100% | 24h@-0.63V | [ |
Fig. 7. (a) Schematic structure of PcCu-O8-Zn (the dashed rectangular indicates the unit cell); partial current (b) and Faradaic (c) efficiency of CO for PcCu-O8-Zn/CNT, PcCu-O8-Cu/CNT, PcZn-O8-Zn/CNT and PcZn-O8-Cu/CNT at different potentials. (a?c) Reprinted with permission from Ref. [77]. Copyright 2020, the Springer-Nature. (d) Illustration of the preparation of NiPc-NiO4. Faradaic efficiencies (e) of CO, and CO partial current density (f) for NiPc-NiO4 and NiPc-OH. (d?f) Reprinted with permission from Ref. [78]. Copyright 2021, Wiley-VCH. (g) Illustration of the structure of PcCu-Cu-O; CV curves (h) and FEs (i) of C2H4, CH4, CO, and H2 for PcCu-Cu-O. (h,i) Reprinted with permission from Ref. [79]. Copyright 2021, American Chemical Society.
Fig. 8. (a) Design and synthetic scheme for isoreticular MOF series MPc-Cu-X (M = Co, Ni, X = NH, O) containing CoPc and NiPc units connected by Cu bis(diimine) and Cu bis(dioxolene) linkages. Reprinted with permission from Ref. [80]. Copyright 2020, American Chemical Society. (b) Illustration of the preparation for phenanthroline-doped ZIF-8; (c) FECO at various potentials on pristine ZIF-8, ZIF-A-LD, pristine ZIF-8/CB, and ZIF-A-LD/CB. (b,c) Reprinted with permission from Ref. [82]. Copyright 2019, Wiley-VCH. (d) Schematic illustration of the crystal structure of ZIF-8 and CALF20; (e) CO Faradaic efficiencies at different applied potentials for CALF20 and ZIF-8 in 1.0 mol/L KOH. (d,e) Reprinted with permission from Ref. [83]. Copyright 2021, American Chemical Society.
Fig. 9. (a) Scheme illustrating the synthesis of Ag@Al-PMOF hybrids. Reprinted with permission from Ref. [84]. Copyright 2020, Wiley-VCH. (b) Schematics for the Ag nanoparticle incorporated MOF structure. Reprinted with permission from Ref. [85]. Copyright 2020, American Chemical Society. (c) Schematic illustration of the synthetic procedure to obtain Zn-CoTAPc/PMo12 MLSs. Reprinted with permission from Ref. [86]. Copyright 2021, American Chemical Society.
Fig. 10. Structures of Cu8 clusters and unit cell in NNU-33(S) (a) and NNU-33(H) (b). (a,b) Reprinted with permission from Ref. [88]. Copyright 2021, American Chemical Society. (c) Illustration of the solvothermal synthesis of CuHHTP and preparation of Cu2O@CuHHTP via electrochemical treatment of CuHHTP. Reprinted with permission from Ref. [89]. Copyright 2020 Wiley-VCH. (d) Schematic of the two-step reconstruction process, including (1) the electrolyte-mediated chemical and structural transformation from Bi-MOF NR to Bi2O2CO3 NS, and (2) electrochemical reduction of Bi2O2CO3 NS to Bi NS, (e) SEM image for Bi-MOF NR, (f) Bi2O2CO3 NS and (g) TEM image for the final Bi NS. (e?g) Reprinted with permission from Ref. [90]. Copyright 2021 Wiley-VCH.
Catalyst | Cell | Electrolyte | J (mA cm-2) | Product FE | Stability | Ref. |
---|---|---|---|---|---|---|
Cu3(HHTQ)2 | H | 0.1 mol/L KHCO3 | ~0.5 | CH3OH 53.6% | 10h@-0.4V | [ |
PcCu-O8-Zn | H | 0.1 mol/L KHCO3 | ~8 | CO 88% | 10h@-0.7V | [ |
NiPc-NiO4 | H | 0.5 mol/L KHCO3 | 34.5 | CO 98.4% | 10h@-0.85V | [ |
PcCu-Cu-O | H | 0.1 mol/L KOH | 7.3 | C2H4 50% | 4h@-1.2V | [ |
NNU-33(H) | flow | 1 mol/L KOH | 391 | CH4 82% | 5h@-0.9V | [ |
Cu2O@CuHHTP | H | 0.1 mol/L KCl/0.1 mol/L KHCO3 | 10.8 | CH4 73% | 5h@-1.4V | [ |
Bi-MOF | H | 0.1 mol/L KHCO3 | 15 | HCOO‒ 92% | 10h@-1.1V | [ |
Table 3 Comparisons of different MOFs-based catalysts for CO2RR.
Catalyst | Cell | Electrolyte | J (mA cm-2) | Product FE | Stability | Ref. |
---|---|---|---|---|---|---|
Cu3(HHTQ)2 | H | 0.1 mol/L KHCO3 | ~0.5 | CH3OH 53.6% | 10h@-0.4V | [ |
PcCu-O8-Zn | H | 0.1 mol/L KHCO3 | ~8 | CO 88% | 10h@-0.7V | [ |
NiPc-NiO4 | H | 0.5 mol/L KHCO3 | 34.5 | CO 98.4% | 10h@-0.85V | [ |
PcCu-Cu-O | H | 0.1 mol/L KOH | 7.3 | C2H4 50% | 4h@-1.2V | [ |
NNU-33(H) | flow | 1 mol/L KOH | 391 | CH4 82% | 5h@-0.9V | [ |
Cu2O@CuHHTP | H | 0.1 mol/L KCl/0.1 mol/L KHCO3 | 10.8 | CH4 73% | 5h@-1.4V | [ |
Bi-MOF | H | 0.1 mol/L KHCO3 | 15 | HCOO‒ 92% | 10h@-1.1V | [ |
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