电催化氮还原合成氨MOF基催化剂研究进展

doi:10.16085/j.issn.1000-6613.2022-1042

摘要/Abstract

摘要：

室温下电催化氮还原合成氨（nitrogen reduction reaction，NRR）因其较低的能耗而受到广泛关注。到目前为止，设计高效电催化剂以提高NRR性能是研究重点。其中，金属有机骨架（metal organic framework，MOF）及衍生材料因其独特的多孔结构和可控成分等优势促进了其在气体捕获、分离和催化中的应用。本文首先讨论NRR的反应机制，然后重点讨论MOF及衍生材料用作NRR电催化剂的研究进展，最后，对MOF基NRR电催化剂的设计策略、存在问题及NRR催化面临挑战进行了总结与展望。此外，文中指出：① 自支撑MOF基电催化剂的合理设计对NRR性能有质的提升；② 机器学习、DFT计算及原位测试技术的有效结合对NRR机理、催化剂的高效设计及筛选等具有重要指导意义。因此这些也将成为NRR催化未来研究趋势。

关键词: 电化学, 催化剂, 还原, 合成, 金属-有机框架

Abstract:

The production of ammonia by electrocatalytic nitrogen reduction reaction (NRR) at room temperature has attracted extensive attention due to its low energy consumption. So far, the research focus is to design highly efficient electrocatalysts. Metal organic framework (MOF) and their derivatives have wide applications in gas capture, separation, and catalysis due to their unique porous structure and controllable compositions. This review first discusses the mechanism of NRR, and then focuses on the research progress of NRR electrocatalysts of MOF and the derived materials. Finally, we summarize and prospect the design strategy, existing problems of the MOF based NRR electrocatalysts and the challenges in NRR catalysis. In addition, this review points out that: ① The reasonable design of self-supporting MOF electrocatalyst can substantially improve the NRR performance; ② The effective combination of machine learning, DFT calculation and in situ testing technology has important guiding significance for NRR mechanism study, efficient design and screening of catalysts, etc., which will become the future research trends of NRR catalysis.

Key words: electrochemistry, catalyst, reduction, synthesis, metal organic frameworks

中图分类号:

TQ032.4

郭朋举, 何小波, 银凤翔. 电催化氮还原合成氨MOF基催化剂研究进展[J]. 化工进展, 2023, 42(4): 1797-1810.

GUO Pengju, HE Xiaobo, YIN Fengxiang. Research progress in MOF-based catalysts for electrocatalytic nitrogen reduction to ammonia[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1797-1810.

图/表 7

参考文献 69

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催化剂	电解质	氨产率	法拉第效率/%	参考文献
NH₂-MIL-88B-Fe（Fe基MOF）	0.1mol/L Na₂SO₄	1.205×10^-10mol·s^-1·cm^-2	12.45	[22]
Cu@Ce-MOF-2（铜网原位生长Ce-MOF）	0.1mol/L KOH	14.83μg·h^-1·cm^-2	10.81	[23]
Defective UiO-66-NH₂（缺陷型UiO-66-NH₂）	0.1mol/L Na₂SO₄	2.071×10^-10mol·s^-1·cm^-2	85.21	[24]
Fe-MOF（MIL-101-Fe）	2mol/L KOH	2.12×10^-9mol·s^-1·cm^-2	1.43	[25]
HKUST-1（MOF：铜-BTC）	0.1mol/L Na₂SO₄	46.63μg·h^-1·mg_cat^-1	2.45	[26]
Cu^Ⅱ MOF（碳布自支撑Cu^Ⅱ-MOF催化剂）	1mol/L Na₂SO₄	24.7mg·h^-1·mg_cat^-1	11.9	[27]
Co₃HHTP₂（Co₃（六羟基三苯）₂纳米粒子）	0.5mol/L LiClO₄	22.14μg·h^-1·mg_cat^-1	3.34	[29]
MIL-100-Al（Al基MOF）	0.1mol/L KOH	10.6μg·h^-1·cm^-2·mg_cat^-1	22.6	[32]
UiO-66-HAc（缺陷型UiO-66）	0.1mol/L Na₂SO₄	31.81μg·h^-1·mg_cat^-1	48.06	[33]
Co₃Fe-MOF（二维双金属MOF纳米片）	0.1mol/L KOH	8.79μg·h^-1·mg_cat^-1	25.64	[36]
NiFe-MOF（零维双金属MOF）	0.1mol/L NaHCO₃	9.3μg·h^-1mg_cat^-1	11.5	[37]
MoS₂@ZIF-71（ZIF-71封装MoS₂纳米花）	0.1mol/L Na₂SO₄	56.69μg·h^-1·mg_cat^-1	30.91	[40]
CNT@CAU-17（碳纳米管插入CAU-17）	0.05mol/L H₂SO₄	11.92μg·h^-1·mg_cat^-1	31.27	[41]
MIL-101（Fe）/MoS₃（纳米片杂化材料）	0.1mol/L HCl	25.7μg·h^-1·mg_cat^-1	36.71	[42]
Ag-Au@ZIF（ZIF-71封装Ag-Au）	0.2mol/L LiCF₃SO₃	0.623μg·h^-1·cm^-2	18	[43]
AuCu/ZIF-8（AuCu纳米合金负载ZIF-8）	0.1mol/L HCl	63.9μg·h^-1·mg_cat^-1	14.2	[44]
HT Au@MOF（疏水性MOF自支撑Au）	0.1mol/L Na₂SO₄	49.5μg·h^-1·mg_cat^-1	60.9	[45]
Pt/Au@ZIF（ZIF-71封装Pt/Au）	0.2mol/L LiCF₃SO₃	161μg·h^-1·mg_cat^-1	44	[46]
Au@ZIF-8（纳米金嵌入ZIF-8）	0.1mol/L Na₂SO₄	28.7μg·h^-1·cm^-2	44	[47]

催化剂	电解质	氨产率	法拉第效率/%	参考文献
NH₂-MIL-88B-Fe（Fe基MOF）	0.1mol/L Na₂SO₄	1.205×10^-10mol·s^-1·cm^-2	12.45	[22]
Cu@Ce-MOF-2（铜网原位生长Ce-MOF）	0.1mol/L KOH	14.83μg·h^-1·cm^-2	10.81	[23]
Defective UiO-66-NH₂（缺陷型UiO-66-NH₂）	0.1mol/L Na₂SO₄	2.071×10^-10mol·s^-1·cm^-2	85.21	[24]
Fe-MOF（MIL-101-Fe）	2mol/L KOH	2.12×10^-9mol·s^-1·cm^-2	1.43	[25]
HKUST-1（MOF：铜-BTC）	0.1mol/L Na₂SO₄	46.63μg·h^-1·mg_cat^-1	2.45	[26]
Cu^Ⅱ MOF（碳布自支撑Cu^Ⅱ-MOF催化剂）	1mol/L Na₂SO₄	24.7mg·h^-1·mg_cat^-1	11.9	[27]
Co₃HHTP₂（Co₃（六羟基三苯）₂纳米粒子）	0.5mol/L LiClO₄	22.14μg·h^-1·mg_cat^-1	3.34	[29]
MIL-100-Al（Al基MOF）	0.1mol/L KOH	10.6μg·h^-1·cm^-2·mg_cat^-1	22.6	[32]
UiO-66-HAc（缺陷型UiO-66）	0.1mol/L Na₂SO₄	31.81μg·h^-1·mg_cat^-1	48.06	[33]
Co₃Fe-MOF（二维双金属MOF纳米片）	0.1mol/L KOH	8.79μg·h^-1·mg_cat^-1	25.64	[36]
NiFe-MOF（零维双金属MOF）	0.1mol/L NaHCO₃	9.3μg·h^-1mg_cat^-1	11.5	[37]
MoS₂@ZIF-71（ZIF-71封装MoS₂纳米花）	0.1mol/L Na₂SO₄	56.69μg·h^-1·mg_cat^-1	30.91	[40]
CNT@CAU-17（碳纳米管插入CAU-17）	0.05mol/L H₂SO₄	11.92μg·h^-1·mg_cat^-1	31.27	[41]
MIL-101（Fe）/MoS₃（纳米片杂化材料）	0.1mol/L HCl	25.7μg·h^-1·mg_cat^-1	36.71	[42]
Ag-Au@ZIF（ZIF-71封装Ag-Au）	0.2mol/L LiCF₃SO₃	0.623μg·h^-1·cm^-2	18	[43]
AuCu/ZIF-8（AuCu纳米合金负载ZIF-8）	0.1mol/L HCl	63.9μg·h^-1·mg_cat^-1	14.2	[44]
HT Au@MOF（疏水性MOF自支撑Au）	0.1mol/L Na₂SO₄	49.5μg·h^-1·mg_cat^-1	60.9	[45]
Pt/Au@ZIF（ZIF-71封装Pt/Au）	0.2mol/L LiCF₃SO₃	161μg·h^-1·mg_cat^-1	44	[46]
Au@ZIF-8（纳米金嵌入ZIF-8）	0.1mol/L Na₂SO₄	28.7μg·h^-1·cm^-2	44	[47]

催化剂	电解质	氨产率	法拉第效率/%	参考文献
Co@NC（Co纳米粒子负载氮掺杂碳基底）	0.1mol/L Na₂SO₄	1.57×10^-11mol·s^-1·cm^-2	21.79	[48]
Co/C-900（钴掺杂碳复合材料）	0.1mol/L KOH	4.66μmol·h^-1·cm^-2	11.53	[49]
Bi NPs@CRs（原位衍生铋纳米粒子）	0.1mol/L HCl	20.80μg·h^-1·mg_cat^-1	11.50	[50]
Zn-Co₃O₄（Zn掺杂Co₃O₄纳米多面体）	0.1mol/L HCl	22.71μg·h^-1·mg_cat^-1	11.9	[51]
Co₃O₄@NCs（氮掺杂碳/Co₃O₄核壳结构）	0.05mol/L H₂SO₄	42.58μg·h^-1·mg_cat^-1	8.5	[52]
Fe₂O₃@MoS₂（双金属杂化材料）	0.1mol/L Na₂SO₄	112.15μg·h^-1·mg_cat^-1	8.62	[53]
Fe_1.89 Mo_4.11O₇/FeS₂@C（双金属杂化材料）	0.1mol/L KOH	105.3μg·h^-1·mg_cat^-1	54.7	[54]
Mo-Co/NC（Mo-Co嵌入氮掺杂碳基底）	0.1mol/L Na₂SO₄	89.8μmol·h^-1·mg_cat^-1	13.5	[55]
CoRu@NC（双金属氮掺杂碳杂化材料）	0.1mol/L KOH	56.82μg·h^-1·mg_cat^-1	2.02	[56]
CoP HNC（中空磷化钴纳米笼）	0.1mol/L Na₂SO₄	10.78μg·h^-1·mg_cat^-1	7.36	[57]
MoFe-Pc微球（Pc磷掺杂碳）	0.1mol/L HCl	34.23μg·h^-1·mg_cat^-1	16.83	[58]
Ru SAc/N-C（Ru单原子催化剂）	0.05mol/L H₂SO₄	120.9μg·h^-1·mg_cat^-1	29.6	[59]
Ni-N _x -C（Ni单原子催化剂）	0.5mol/L LiClO₄	115μg·h^-1·cm^-2	21.9	[60]
ISAS-Fe/NC（Fe单原子催化剂）	0.1mol/L PBS	62.9μg·h^-1·mg_cat^-1	18.6	[61]
Co/N-doped C（钴/氮掺杂碳材料）	0.1mol/L KOH	0.4μmol·h^-1·cm^-2	10.1	[62]
Ru@ZrO₂/NC（添加ZrO₂的Ru单原子催化剂）	0.1mol/L HCl	3.665mg·h^-1·mg_Ru^-1	21	[63]
Fe₁-N-C（Fe单原子嵌入氮掺杂碳基底）	0.1mol/L HCl	1.56×10^-11mol·s^-1·cm^-2	4.51	[64]
NPC-750（氮掺杂多孔炭）	0.05mol/L H₂SO₄	23.8μg·h^-1·mg_cat^-1	1.42	[65]
C-ZIF-1100-1h（氮掺杂纳米多孔炭）	0.1mol/L Na₂SO₄	3.4×10^-6mol·cm^-2·h^-1	10.2	[66]
NP-C-MOF-5（氮、磷共掺杂多孔炭）	0.1mol/L HCl	1.08μg·h^-1·mg_cat^-1	0.52	[67]
S/N-MPC（硫改性的氮掺杂多孔炭）	0.05mol/L H₂SO₄	45.51μg·h^-1·mg_cat^-1	25.16	[68]

催化剂	电解质	氨产率	法拉第效率/%	参考文献
Co@NC（Co纳米粒子负载氮掺杂碳基底）	0.1mol/L Na₂SO₄	1.57×10^-11mol·s^-1·cm^-2	21.79	[48]
Co/C-900（钴掺杂碳复合材料）	0.1mol/L KOH	4.66μmol·h^-1·cm^-2	11.53	[49]
Bi NPs@CRs（原位衍生铋纳米粒子）	0.1mol/L HCl	20.80μg·h^-1·mg_cat^-1	11.50	[50]
Zn-Co₃O₄（Zn掺杂Co₃O₄纳米多面体）	0.1mol/L HCl	22.71μg·h^-1·mg_cat^-1	11.9	[51]
Co₃O₄@NCs（氮掺杂碳/Co₃O₄核壳结构）	0.05mol/L H₂SO₄	42.58μg·h^-1·mg_cat^-1	8.5	[52]
Fe₂O₃@MoS₂（双金属杂化材料）	0.1mol/L Na₂SO₄	112.15μg·h^-1·mg_cat^-1	8.62	[53]
Fe_1.89 Mo_4.11O₇/FeS₂@C（双金属杂化材料）	0.1mol/L KOH	105.3μg·h^-1·mg_cat^-1	54.7	[54]
Mo-Co/NC（Mo-Co嵌入氮掺杂碳基底）	0.1mol/L Na₂SO₄	89.8μmol·h^-1·mg_cat^-1	13.5	[55]
CoRu@NC（双金属氮掺杂碳杂化材料）	0.1mol/L KOH	56.82μg·h^-1·mg_cat^-1	2.02	[56]
CoP HNC（中空磷化钴纳米笼）	0.1mol/L Na₂SO₄	10.78μg·h^-1·mg_cat^-1	7.36	[57]
MoFe-Pc微球（Pc磷掺杂碳）	0.1mol/L HCl	34.23μg·h^-1·mg_cat^-1	16.83	[58]
Ru SAc/N-C（Ru单原子催化剂）	0.05mol/L H₂SO₄	120.9μg·h^-1·mg_cat^-1	29.6	[59]
Ni-N _x -C（Ni单原子催化剂）	0.5mol/L LiClO₄	115μg·h^-1·cm^-2	21.9	[60]
ISAS-Fe/NC（Fe单原子催化剂）	0.1mol/L PBS	62.9μg·h^-1·mg_cat^-1	18.6	[61]
Co/N-doped C（钴/氮掺杂碳材料）	0.1mol/L KOH	0.4μmol·h^-1·cm^-2	10.1	[62]
Ru@ZrO₂/NC（添加ZrO₂的Ru单原子催化剂）	0.1mol/L HCl	3.665mg·h^-1·mg_Ru^-1	21	[63]
Fe₁-N-C（Fe单原子嵌入氮掺杂碳基底）	0.1mol/L HCl	1.56×10^-11mol·s^-1·cm^-2	4.51	[64]
NPC-750（氮掺杂多孔炭）	0.05mol/L H₂SO₄	23.8μg·h^-1·mg_cat^-1	1.42	[65]
C-ZIF-1100-1h（氮掺杂纳米多孔炭）	0.1mol/L Na₂SO₄	3.4×10^-6mol·cm^-2·h^-1	10.2	[66]
NP-C-MOF-5（氮、磷共掺杂多孔炭）	0.1mol/L HCl	1.08μg·h^-1·mg_cat^-1	0.52	[67]
S/N-MPC（硫改性的氮掺杂多孔炭）	0.05mol/L H₂SO₄	45.51μg·h^-1·mg_cat^-1	25.16	[68]

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