d区过渡金属基催化剂用于电化学合成氨

doi:10.16085/j.issn.1000-6613.2020-1949

摘要/Abstract

摘要：

d区过渡金属基（d-TMs）材料易于改性，且因其空的d轨道有利于吸附氮气（N₂），分离的d电子可以供给N₂，被认为是理想的电化学合成氨（NRR）催化剂，在近年的深入研究中取得长足进展。本文综述了近几年改性d-TMs基材料应用于NRR的研究报道，简述了基于d-TMs基催化剂的NRR反应机理，并详细总结了表/界面工程、晶面调控与非晶化、缺陷工程、构建仿生位点等改性策略指导设计的d-TMs基NRR催化剂，重点分析了每种改性策略对NRR性能的影响。最后对该领域的发展前景进行了展望，从理论计算模型、催化剂改性、电化学体系、测试及表征手段、氨气（NH₃）检测手段等角度进一步提出了今后需要关注的问题，为改性d-TMs基高效NRR催化剂的设计提供了参考。

关键词: 电化学, 合成, 活性, 催化剂

Abstract:

d-Block transition metals (d-TMs) are considered to be an ideal candidate for electrocatalytic nitrogen reduction reaction (NRR) catalysts because they are easy to be modified. Meanwhile, they possess unfilled valence d orbitals, which are conducive to adsorbing nitrogen (N₂), as well as separated d electrons can donate into N₂ Consequently, considerable progress of d-TMs in NRR has been acquired in in-depth research. This article reviewed the latest researches on the applications of d-TMs based materials, which were designed and synthesized by different modification strategies to NRR. The NRR mechanisms based on d-TMs catalysts were briefly described. Moreover, the d-TMs based NRR catalysts designed by modification strategies such as surface/interface engineering, crystal facet regulation/amorphization, defect engineering, as well as the construction of bionic site, were summarized in detail and the influence of each modification strategy on NRR performance was analyzed. Finally, this article prospected the development prospects of this field and proposed the problems that need to be paid attention in the future from a series of perspectives, e.g., theoretical calculation model, catalyst modification strategies, electrochemical system, testing and characterization methods, and ammonia (NH₃) detection methods, so as to provide references for the design of modified d-TMs based efficient NRR catalysts.

Key words: electrochemistry, synthesis, reactivity, catalyst

中图分类号:

TB324

赵斐, 王琪, 刘光, 李晋平. d区过渡金属基催化剂用于电化学合成氨[J]. 化工进展, 2021, 40(4): 1948-1965.

ZHAO Fei, WANG Qi, LIU Guang, LI Jinping. d-Block transition metal-based catalysts for electrocatalytic ammonia synthesis[J]. Chemical Industry and Engineering Progress, 2021, 40(4): 1948-1965.

图/表 11

参考文献 120

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催化剂	电解液	电位/V_RHE	法拉第效率/%	氨产率	参考文献
Ru₂P-rGO	0.1mol·L^-1 HCl	-0.05	13.04	32.8μg·h^-1·mg_cat^-1	[41]
Mo₂C/C	0.5mol·L^-1 Li₂SO₄	-0.3	7.8	3.7μg·h^-1·mg_cat^-1	[43]
Mo⁰/GDY	0.1mol·L^-1 Na₂SO₄	-1.2(vs.SCE)	21	145.4μg·h^-1·mg_cat^-1	[44]
SA-Mo/NPC	0.1mol·L^-1 KOH	-0.3	14.6±1.6	(34.0±3.6)μg·h^-1·mg_cat^-1	[51]
SA-Mo/NPC	0.1mol·L^-1 HCl	-0.25	6.8±0.3	(31.5±1.2)μg·h^-1·mg_cat^-1	[51]
Cu SAC	0.1mol·L^-1 KOH	-0.35	13.8	53.3μg·h^-1·mg_cat^-1	[52]
Cu SAC	0.1mol·L^-1 HCl	-0.3	11.7	49.3μg·h^-1·mg_cat^-1	[52]
Ru SAs/N-C	0.05mol·L^-1 H₂SO₄	-0.2	29.6	120.9μg·h^-1·mg_cat^-1	[53]
Y₁/NC	0.1mol·L^-1 HCl	-0.1	12.1	23.2μg·h^-1·cm^-2	[56]
Sc₁/NC	0.1mol·L^-1 HCl	-0.1	11.2	20.4μg·h^-1·cm^-2	[56]
Fe_SA-N-C	0.1mol·L^-1 KOH	0	56.55	7.48μg·h^-1·mg_cat^-1	[57]
SACs-MoS₂-Fe	0.1mol·L^-1 KCl	-0.2	31.6±2	(97.5±6)μg·h^-1·cm^-2	[45]
AuHNCs	0.5mol·L^-1 LiClO₄	-0.4	30.2		[46]
AuHNCs	0.5mol·L^-1 LiClO₄	-0.5		3.9μg·h^-1·cm^-2	[46]
Rh NNs	0.1mol·L^-1 KOH	-0.2	0.217	23.88μg·h^-1·mg_cat^-1	[47]
Dendritic Cu	0.1mol·L^-1 HCl	-0.4	15.12	25.63μg·h^-1·mg_cat^-1	[62]
Mo₂C	0.1mol·L^-1 HCl	-0.3	8.13	95.1μg·h^-1·mg_cat^-1	[63]
Cr₂O₃ MHCMs	0.1mol·L^-1 Na₂SO₄	-0.9	6.78	25.3μg·h^-1·cm^-2	[48]
Cr₂O₃nanofibers	0.1mol·L^-1 HCl	-0.75	8.56	28.13μg·h^-1·mg_cat^-1	[64]
NPG@ZIF-8	0.1mol·L^-1 Na₂SO₄	-0.6	44		[66]
NPG@ZIF-8	0.1mol·L^-1 Na₂SO₄	-0.8		(28.7±0.9)μg·h^-1·mg_cat^-1	[66]
Au-Fe₃O₄ NPs	0.1mol·L^-1 KOH	-0.2	10.54	21.42μg·h^-1·mg_cat^-1	[67]
C@NiO@Ni	0.1mol·L^-1 KOH	-0.7	10.9	43.15μg·h^-1·mg_cat^-1	[70]
CoS₂/NS-G	0.05mol·L^-1 H₂SO₄	-0.05	25.9		[71]
CoS₂/NS-G	0.05mol·L^-1 H₂SO₄	-0.2		25.0μg·h^-1·mg_cat^-1	[71]
Fe₃C@C	0.05mol·L^-1 H₂SO₄	-0.2	9.15	8.53μg·h^-1·mg_cat^-1	[2]
Cu/PI-300	0.1mol·L^-1 KOH	-0.3	6.56		[68]
Cu/PI-300	0.1mol·L^-1 KOH	-0.4		17.2μg·h^-1·cm^-2	[68]
FeNi-LDH	0.1mol·L^-1 Na₂SO₄	-0.5	23	10.53μg·h^-1·cm^-2	[74]
C@CoS@TiO₂	0.1mol·L^-1 Na₂SO₄	-0.55	28.6	49.51μg·h^-1·cm^-2	[69]

催化剂	电解液	电位/V_RHE	法拉第效率/%	氨产率	参考文献
Ru₂P-rGO	0.1mol·L^-1 HCl	-0.05	13.04	32.8μg·h^-1·mg_cat^-1	[41]
Mo₂C/C	0.5mol·L^-1 Li₂SO₄	-0.3	7.8	3.7μg·h^-1·mg_cat^-1	[43]
Mo⁰/GDY	0.1mol·L^-1 Na₂SO₄	-1.2(vs.SCE)	21	145.4μg·h^-1·mg_cat^-1	[44]
SA-Mo/NPC	0.1mol·L^-1 KOH	-0.3	14.6±1.6	(34.0±3.6)μg·h^-1·mg_cat^-1	[51]
SA-Mo/NPC	0.1mol·L^-1 HCl	-0.25	6.8±0.3	(31.5±1.2)μg·h^-1·mg_cat^-1	[51]
Cu SAC	0.1mol·L^-1 KOH	-0.35	13.8	53.3μg·h^-1·mg_cat^-1	[52]
Cu SAC	0.1mol·L^-1 HCl	-0.3	11.7	49.3μg·h^-1·mg_cat^-1	[52]
Ru SAs/N-C	0.05mol·L^-1 H₂SO₄	-0.2	29.6	120.9μg·h^-1·mg_cat^-1	[53]
Y₁/NC	0.1mol·L^-1 HCl	-0.1	12.1	23.2μg·h^-1·cm^-2	[56]
Sc₁/NC	0.1mol·L^-1 HCl	-0.1	11.2	20.4μg·h^-1·cm^-2	[56]
Fe_SA-N-C	0.1mol·L^-1 KOH	0	56.55	7.48μg·h^-1·mg_cat^-1	[57]
SACs-MoS₂-Fe	0.1mol·L^-1 KCl	-0.2	31.6±2	(97.5±6)μg·h^-1·cm^-2	[45]
AuHNCs	0.5mol·L^-1 LiClO₄	-0.4	30.2		[46]
AuHNCs	0.5mol·L^-1 LiClO₄	-0.5		3.9μg·h^-1·cm^-2	[46]
Rh NNs	0.1mol·L^-1 KOH	-0.2	0.217	23.88μg·h^-1·mg_cat^-1	[47]
Dendritic Cu	0.1mol·L^-1 HCl	-0.4	15.12	25.63μg·h^-1·mg_cat^-1	[62]
Mo₂C	0.1mol·L^-1 HCl	-0.3	8.13	95.1μg·h^-1·mg_cat^-1	[63]
Cr₂O₃ MHCMs	0.1mol·L^-1 Na₂SO₄	-0.9	6.78	25.3μg·h^-1·cm^-2	[48]
Cr₂O₃nanofibers	0.1mol·L^-1 HCl	-0.75	8.56	28.13μg·h^-1·mg_cat^-1	[64]
NPG@ZIF-8	0.1mol·L^-1 Na₂SO₄	-0.6	44		[66]
NPG@ZIF-8	0.1mol·L^-1 Na₂SO₄	-0.8		(28.7±0.9)μg·h^-1·mg_cat^-1	[66]
Au-Fe₃O₄ NPs	0.1mol·L^-1 KOH	-0.2	10.54	21.42μg·h^-1·mg_cat^-1	[67]
C@NiO@Ni	0.1mol·L^-1 KOH	-0.7	10.9	43.15μg·h^-1·mg_cat^-1	[70]
CoS₂/NS-G	0.05mol·L^-1 H₂SO₄	-0.05	25.9		[71]
CoS₂/NS-G	0.05mol·L^-1 H₂SO₄	-0.2		25.0μg·h^-1·mg_cat^-1	[71]
Fe₃C@C	0.05mol·L^-1 H₂SO₄	-0.2	9.15	8.53μg·h^-1·mg_cat^-1	[2]
Cu/PI-300	0.1mol·L^-1 KOH	-0.3	6.56		[68]
Cu/PI-300	0.1mol·L^-1 KOH	-0.4		17.2μg·h^-1·cm^-2	[68]
FeNi-LDH	0.1mol·L^-1 Na₂SO₄	-0.5	23	10.53μg·h^-1·cm^-2	[74]
C@CoS@TiO₂	0.1mol·L^-1 Na₂SO₄	-0.55	28.6	49.51μg·h^-1·cm^-2	[69]

催化剂	电解液	电位/V_RHE	法拉第效率/%	氨产率	参考文献
Au THH NR	0.1mol·L^-1 KOH	-0.2	4	1.648μg·h^-1·cm^-2	[11]
Nb₂O₅	0.1mol·L^-1 HCl	-0.55	9.26	43.6μg·h^-1·mg_cat^-1	[80]
a-Au/CeO_x-RGO	HCl(pH=1)	-0.2	10.10	8.3μg·h^-1·mg_cat^-1	[9]
Pd_0.2Cu_0.8/rGO	0.1mol·L^-1 KOH	0	约4.3		[82]
		-0.2		2.80μg·h^-1·mg_cat^-1
Ir-Te	1.0mol·L^-1 KOH	-0.2	15.3	51.1μg·h^-1·mg_cat^-1	[76]

催化剂	电解液	电位/V_RHE	法拉第效率/%	氨产率	参考文献
Au THH NR	0.1mol·L^-1 KOH	-0.2	4	1.648μg·h^-1·cm^-2	[11]
Nb₂O₅	0.1mol·L^-1 HCl	-0.55	9.26	43.6μg·h^-1·mg_cat^-1	[80]
a-Au/CeO_x-RGO	HCl(pH=1)	-0.2	10.10	8.3μg·h^-1·mg_cat^-1	[9]
Pd_0.2Cu_0.8/rGO	0.1mol·L^-1 KOH	0	约4.3		[82]
		-0.2		2.80μg·h^-1·mg_cat^-1
Ir-Te	1.0mol·L^-1 KOH	-0.2	15.3	51.1μg·h^-1·mg_cat^-1	[76]

催化剂	电解液	电位/V_RHE	法拉第效率/%	氨产率	参考文献
Au_x/Ni	0.05mol·L^-1 H₂SO₄	-0.14	67.8	7.4μg·h^-1·mg_cat^-1	[84]
Pd₃Cu₁	1mol·L^-1 KOH	-0.05	1.56		[89]
Pd₃Cu₁	1mol·L^-1 KOH	-0.25		39.9μg·h^-1·mg_cat^-1	[89]
Fe-W₁₈O₄₉	0.25mol·L^-1 LiClO₄	-0.15	20	24.7μg·h^-1·mg_cat^-1	[90]
Fe-Ni₂P	0.1mol·L^-1 HCl	-0.3	7.92	88.51μg·h^-1·mg_cat^-1	[91]
Fe-CeO₂	0.5mol·L^-1 LiClO₄	-0.4	14.7		[92]
Fe-CeO₂	0.5mol·L^-1 LiClO₄	-0.5		26.2μg·h^-1·mg_cat^-1	[92]
Au-TiO₂	0.1mol·L^-1 HCl	-0.2	8.11	21.4μg·h^-1·mg_cat^-1	[59]
Fe-TiO₂	0.5mol·L^-1 LiClO₄	-0.4	25.6	25.47μg·h^-1·mg_cat^-1	[93]
V-TiO₂	0.5mol·L^-1 LiClO₄	-0.4	15.3		[94]
V-TiO₂	0.5mol·L^-1 LiClO₄	-0.5		17.73μg·h^-1·mg_cat^-1	[94]
B-TiO₂	0.1mol·L^-1 Na₂SO₄	-0.8	3.4	14.4μgμg·h^-1·mg_cat^-1	[95]
C-TiO₂	0.1mol·L^-1 Na₂SO₄	-0.7	1.84	16.22μg·h^-1·mg_cat^-1	[96]
C-Ti_xO_y/C	0.1mol·L^-1 LiClO₄	-0.4	17.8	14.8μg·h^-1·mg_cat^-1	[97]
np-PdH_0.43	0.1mol·L^-1 PBS	-0.15	43.6	20.4μg·h^-1·mg_cat^-1	[85]
MXene/SSM	0.01mol·L^-1 HCl	-0.1	4.62	4.72μg·h^-1·cm^-2	[86]
Ti₃C₂T_x(T=F,OH)	0.1mol·L^-1 HCl	-0.4	9.3	20.4μg·h^-1·mg_cat^-1	[99]
TiO₂/Ti₃C₂T_x	0.1mol·L^-1 HCl	-0.45	2.8		[100]
TiO₂/Ti₃C₂T_x	0.1mol·L^-1 HCl	-0.55		32.17μg·h^-1·mg_cat^-1	[100]
Co₃O₄@NC	0.05mol·L^-1 H₂SO₄	-0.2	8.5	42.58μg·h^-1·mg_cat^-1	[102]
TiO₂/Ti	0.1mol·L^-1 Na₂SO₄	-0.6	3.34		[104]
TiO₂/Ti	0.1mol·L^-1 Na₂SO₄	-0.7	2.5	5.61μg·h^-1·cm^-2	[104]
TiO₂(Vo)_800	0.1mol·L^-1 HCl	-0.12	6.5	3μg·h^-1·mg_cat^-1	[105]
d-TiO₂/Ti	0.1mol·L^-1 HCl	-0.15	9.17	7.59μg·h^-1·cm^-2	[106]
Ti³⁺-TiO_2-_x/TM	0.1mol·L^-1 Na₂SO₄	-0.55	14.62	2.15μg·h^-1·cm^-2	[107]
OV-TiO₂-400	0.005mol·L^-1 H₂SO₄	-0.7	5.3		[108]
OV-TiO₂-400	0.005mol·L^-1 H₂SO₄	-0.8		35.6μg·h^-1·mg_cat^-1	[108]
0.57Mn₃O₄/b-TiO₂	0.1mol·L^-1 KOH	-0.35	15		[109]
0.57Mn₃O₄/b-TiO₂		-0.45		9.85μg·h^-1·cm^-2
0.57SnO₂/b-TiO₂		-0.45	21.3	13.4μg·h^-1·cm^-2
DR MoS₂	0.1mol·L^-1 Na₂SO₄	-0.4	8.34	29.28μg·h^-1·mg_cat^-1	[111]
Co-doped MoS_2-_x	0.01mol·L^-1 H₂SO₄	-0.3	10	10.71μg·h^-1·mg_cat^-1	[87]
VN/TM	0.1mol·L^-1 HCl	-0.5	2.25	5.14μg·h^-1·cm^-2	[112]
W₂N₃	0.1mol·L^-1 KOH	-0.2	11.67	11.66μg·h^-1·mg_cat^-1	[113]
MV-MoN@NC	0.1mol·L^-1 HCl	-0.2	6.9	76.9μg·h^-1·mg_cat^-1	[114]