Multiscale optimization design of porphyrin electrocatalysts for redox reactions under operational conditions

doi:10.1016/S1872-2067(26)65171-6

Chinese Journal of Catalysis ›› 2026, Vol. 90: 52-81.DOI: 10.1016/S1872-2067(26)65171-6

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Multiscale optimization design of porphyrin electrocatalysts for redox reactions under operational conditions

Mingyi Zhao^a^,¹, Zhengyang Liu^a^,¹, Cong Yang^a^,¹, Zhaodi He^a, Yujun Guo^a, Rui Cai^a, Xiangqian Yin^c, Jianwei Wang^c, Xueqin Mu^a, Suli Liu^a^,^*(), Dingsheng Wang^b^,^*(), Zhihui Dai^a

^a School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, Jiangsu, China
^b Department of Chemistry, Tsinghua University, Beijing 100084, China
^c China GRINM Group Co. Ltd., Beijing 100088, China

Received:2026-02-08 Accepted:2026-03-22 Online:2026-11-05 Published:2026-09-09
About author:Sui Liu (School of Chemistry and Molecular Engineering, Nanjing Tech University) received her PhD from the Nanjing Normal University in 2014. She joined Nanjing Xiaozhuang University where she became a full professor. Currently, she works at the School of Chemistry and Molecular Engineering, Nanjing Tech University. Her research focuses on new energy materials, water-splitting electrocatalysts, and other related fields of electrochemical catalysis.
Dingsheng Wang (Department of Chemistry, Tsinghua University) received his BS degree from the Department of Chemistry and Physics at the University of Science and Technology of China in 2004, and his PhD degree from the Department of Chemistry at Tsinghua University in 2009 under the supervision of Prof. Yadong Li. He conducted his postdoctoral research in Prof. Shoushan Fan's group at the Department of Physics, Tsinghua University. He joined the faculty of the Department of Chemistry, Tsinghua University, in 2012. His research interests focus on the synthesis and applications of nanomaterials, clusters, and single-atom and dual-atom site catalysts.
First author contact:
¹Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22234005);National Natural Science Foundation of China(22494632);Joint Funds of the National Natural Science Foundation of China(U25A20581);Major Basic Research Project of the Natural Science Foundation of the Jiangsu Higher Education Institutions(25KJA150002);Jiangsu Provincial University Key Laboratory of Intelligent Medical Sensing Materials and Devices

Abstract

Abstract:

Porphyrin electrocatalysts possess significant advantages, including adjustable structure, high selectivity, and excellent stability, and are widely applied in redox reactions. However, under actual operating conditions, porphyrin catalysts are prone to structural rearrangement and loss of active sites, resulting in decreased activity and stability, and making it difficult to meet the requirements of industrial applications. Based on the current status of porphyrin catalysts from theoretical research to industrial application, this review aims to clarify the design and application strategies of them under actual operating conditions. Firstly, we provide an overview of the classification system of porphyrin catalysts. Secondly, we delve into the challenges faced by porphyrin catalysts in industrial environments. Subsequently, we propose optimization strategies for porphyrin electrocatalysts at the atomic scale (strongly coupled carrier and spatial confinement) and the molecular scale (regulation of large ring conjugation, strengthening metal-ligand bonds and mass transfer channels), and cover their practical applications. Finally, we focus on integrated electrodes suitable for industrial implementation. We systematically summarize the main challenges and solutions faced by porphyrin electrocatalysts under actual working conditions, and outline the future development directions.

Key words: Porphyrin electrocatalysts, Redox reactions, Multiscale regulation, Industrial-scale production

Mingyi Zhao, Zhengyang Liu, Cong Yang, Zhaodi He, Yujun Guo, Rui Cai, Xiangqian Yin, Jianwei Wang, Xueqin Mu, Suli Liu, Dingsheng Wang, Zhihui Dai. Multiscale optimization design of porphyrin electrocatalysts for redox reactions under operational conditions[J]. Chinese Journal of Catalysis, 2026, 90: 52-81.

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Figures/Tables 15

Fig. 1. Schematic diagram of multi-scale optimization design of porphyrin electrocatalysts for redox reactions.

Fig. 2. Progress chart on the application of porphyrin catalysts. Reproduced with permission: Copyright, 2016, Wiley-VCH Verlag GmbH [102]; Copyright, 2017, Wiley‐VCH Verlag GmbH [103]; Copyright, 2018, American Chemical Society [104]; Copyright, 2019, Phys. Chem. Phys [105]; Copyright, 2020 Royal Society of Chemistry [106]; Copyright, 2023 Wiley‐VCH GmbH [107]; Copyright, 2024, Wiley-VCH GmbH [108]; Copyright, 2025 Wiley‐VCH GmbH [109].

Fig. 3. (a) The molecular structures of FeP and N18C6-FeP. (b) LSVs of 0.5 mmol L-1 N18C6-FeP in DMF under CO2 with the addition of Na. (c) LSVs of 0.5 mmol L-1 N18C6-FeP in DMF under CO2 with the addition of K. Ref. [122], Copyright, 2021, Chinese Journal of Catalysis. (d) Protonation of the appended guanidyl group of 1 in pH ≤ 7 aqueous solutions. (e) FE for the production of CO and H2. Ref. [123], Copyright, 2023. Chinese Journal of Catalysis. (f) Illustration of the fabrication process. (g) Yields and FEs. Ref. [125], Copyright, 2022 Elsevier.

Fig. 4. (a) Schematic diagram. (b) The plot of the oxidation peak and reduction peak potentials versus the logarithm of scan rates on CoPCOP@CNT. (c) Yields and Fes. Reprinted with permission from Ref. [59]. Copyright, 2021, Elsevier. (d) The structure of CoTPP (X = N), CoOTPP (X = O), and CoSTPP (X = S), and the process of compounding them with composite CNTs. (e) Free energy barrier in key steps. Ref. [128]. Copyright, 2022, Elsevier. (f) Potential-dependent NH3 yield rate and FE. (g) Synthesis of the template-pyrolysis method. (h) FECO. (i) ECSA curves. Ref. [129]. Copyright, 2022, Elsevier. (j) Synthesis diagrams of different catalysts. (k) The relative energy diagrams. (l) FE of carbon monoxide calculated. Ref. [130]. Copyright, 2021, American Chemical Society.

Fig. 5. (a) Free-energy diagram. (b) Yield rates and FEs. (c) Yield rates and FEs. Ref. [136]. Copyright, 2025, John Wiley and Sons. (d) Plots of electron density. (e) FEs. (f) Partial current densities. Ref. [137]. Copyright, 2024, John Wiley and Sons. (g) Schematic representation of the synthesis method. (h) Partial current density. Ref. [138]. Copyright, 2025, Royal Society of Chemistry. (i) Synthesis process. (j) In situ ATR-SEIRAS spectra. Ref. [140]. Copyright, 2021, American Chemical Society.

Fig. 6. (a) Free energy diagrams. (b) OER LSV data. Ref. [145]. Copyright, 2024, John Wiley and Sons. (c) Calculated relative Gibbs free energy profile. Ref. [146]. Copyright, 2024, John Wiley and Sons. (d) The free energy diagram. (e) CO faradaic efficiencies. Ref. [148]. Copyright, 2021, Elsevier.

Fig. 7. (a) Ion concentrations pre- (left) and post-CP test (right), following 24-h impregnation. (b) Initial morphology (left) vs. final morphologies post-CP test in 1 mol L-1 KOH (middle) and 10 m KOH (right). Ref. [39], Copyright, 2024 Wiley‐VCH GmbH. (c) FECO: Hg-CoTPP/NG vs. CoTPP/NG at varied potentials. (d) Stability test at 420 mA cm-2. Ref. [152], Copyright, 2022, American Chemical Society.

Fig. 8. (a) Schematic illustration. (b) Potential energy curves. (c) Electrocatalytic CO2RR performances. Ref. [161], Copyright, 2024, John Wiley and Sons. (d) Schematic of the flow cell fitted with an ion-exchange membrane. (e) Chronoamperometry of Fe-TPPNH2. (f) CO2RR product selectivity of Fe-TPPNH2. Ref. [162], Copyright, 2021, Elsevier. (g) Schematic illustration. (h) Polarization curve. (i) Voltage, FECO, and FEH2 as functions of time when the system operated with 0.5 A current. Ref. [163], Copyright, 2020, Elsevier. (j)Schematic illustration. (k) Gibbs free energy of Pt and Co active sites. (l) LSV graph. Ref. [164], Copyright, 2024, Royal Society of Chemistry.

Fig. 9. (a) The Scheme. (b) In-situ ATR-FTIR spectra of Cu-Tph-COF-Dct during the electrochemical CO2RR. Ref. [165], Copyright, 2021, John Wiley and Sons. (c) Gibbs free energy diagrams. (d) Proposed mechanistic scheme. (e) Long-term stability. Ref. [60], Copyright, 2023, John Wiley and Sons. (f) Operando Raman spectra. (g) Plots of the calibrated surface pH against the applied potential based on the Raman results. (h) FE of Cu2O@Cu-TCPP(Co). Ref. [40], Copyright, 2024, John Wiley and Sons.

Fig. 10. (a) Schematic synthesis diagram. (b) FECO. (c) In-situ ATR-IR. Ref. [181], Copyright, 2023, Royal Society of Chemistry. (d) Schematic illustration. (e) The corresponding energy profles. Ref. [182], Copyright, 2023, Tsinghua University Press. (f) Potential-dependent FEH2O2 and H2O2 production rate in 1.0 mol L-1 KOH in flow cell. (g) Long-term stability. (h) Free energy diagram. Ref. [183], Copyright, 2020, Elsevier.

Fig. 11. (a) Stability of MEA. (b) FEH2O2. (c) WTs for CoTPP@RGO-160 and the reference catalysts. Ref. [184], Copyright, 2024, John Wiley and Sons. (d) Theoretical ORR potentials along different reaction pathways. (e) FEH2O2 and productivity. (f) Relationship between calculated Co-dz2 orbital centre and the *O2 binding energy (EO2) on different HMC models. Ref. [168], Copyright, 2022, Royal Society of Chemistry. (g) Free energy diagram. (h)Time-dependent industrially relevant current density curve. (i) Extended structures of NiTP-CoTAPP (c-axis) and view along the a-axis. Ref. [185], Copyright, 2025, John Wiley and Sons. (j) CP curve. (k) Structure diagrams. (l) Electron density difference diagrams and 2D contour plots of NiFe-TCPP. Ref. [39], Copyright, 2024, John Wiley and Sons.

Fig. 12. (a) FE and current density during the long-term stability test. (b) FEs of different products. (c) Energy barriers for the hydrogenation of *OCCO to *OCCHO. Ref. [204], Copyright, 2025, Royal Society of Chemistry. (d) Chemical structure of Ni/Zn-porphyrin COFs and their monomers. (e) FEs of Ni50/Zn50. (f) Pore size distributions. Ref. [205], Copyright, 2024, American Chemical Society.

Fig. 13. (a) Performance of OER||HER and MOR||HER. (b) The stability of Pt10/Ni-ZrO2-NC. (c) Operando Raman spectra at the OCP and different applied potentials. Ref. [210], Copyright, 2025, Royal Society of Chemistry. (d) Schematic illustration of design and synthesis. (e) Stability of NiPc-azo-H2Pp@CNTs in flow cell at 200 mA cm-2 (f) KIE values. Ref. [211], Copyright, 2024, John Wiley and Sons. (g) Chronoamperometry tests. (h) Density functional theory calculated energy for the formation of *COO adsorbed on CoTAP-CONs, CoTAP-CONs-AR, and CoTAP-iCONs. Ref. [212], Copyright, 2022, John Wiley and Sons.

Fig. 14. (a) Scheme of the structure of the used complexes M(TPP). (b,c) Observed averaged cell voltages (pink diamonds) and FEs for H2 (green), CO (blue) and CH4 (pink) with either MWCNTs (left half of graph) or CB (right half of graph) as carbon support after 1 h of electrolysis at 50 mA cm-2 or 100 mA cm-2. Ref. [217], Copyright, 2024, Royal Society of Chemistry. (d) In-situ ATR-SEIRAS spectra. (e) CO2RR product distribution and the corresponding FE. (f) Illustration of Ec, Ea, tc, ta in an exemplary waveform of PPE. Ref. [219], Copyright, 2024, John Wiley and Sons.

Table 1 Classification of types, performances and applications of porphyrin catalysts discussed in this review.

Porphyrin catalyst	Types of catalysts	Applications	Catalytic performance	Stability	Ref.	Porphyrin catalyst	Types of catalyst	Applications	Catalytic performance	Stability	Ref.
Cu₂O@Cu- TCPP(Co)	Cu/Co- based	CO₂RR	500 mA cm^-2 FE_C2H4: 54 ± 2% FE_C2+: 69 ± 4%	>20 h@300 mA cm^-2	[40]	Pt@Co- NPC-800	Co-based	HER	1.32 A cm^-2 @60 °C 2.34 V	22 h @1.9 V	[164]
DAE-BPy- CoPor	Co-based	CO₂RR	20.1 mA cm^-2@-1.0 V vs. RHE FE_CO : 90.5%	24 h@-0.9 V vs. RHE FE> 80%	[53]	CoT-sp2C-P- COF-COOH	Co-based	HER	0.75 V @57.49 mA cm^-2	—	[186]
Co-PPOLs	Co-based	CO₂RR	-0.9 V vs. RHE FE_CO > 94.2%	>20 h@200 mA cm^-2	[60]	Co-N₃C₁-COF	Co-based	4e^-ORR	η: 0.338 V E_1/2:0.794 V	—	[99]
Co-TQCOF	Co-based	CO₂RR	-1.0 V @-20 mA cm^-2 FE: 93.9%	12 h@FE>80%	[63]	Co-N_x	Co-based	2e^-ORR	FE_H2O2: 85% @500 mA cm^-2	12 h @50 mA cm^-2	[114]
CoPc/ppy/ GDE	Co-based	CO₂RR	—	—	[71]	1-CoZn	Zn/ Co-based	ORR	—	10h@0.44V	[146]
CoCoPCP/ CNT	Co-based	CO₂RR	FE_CO: 94% @0.44 V	24 h@0.55 V	[148]	CoPorF/CNT	Co-based	ORR	464 mA cm^-2@3.32 V	48 h @50mA cm^-2	[168]
EP-CoP/Cu	Co-based	CO₂RR	726 mA cm^-2@0.9 V	—	[161]	Co-TEPP-COP/rGO	Co-based	ORR	1.2V FE_H2O2 > 95%	30 h @50 mA cm^-2	[183]
Vg-Por(Co)-MOF	Co-based	CO₂RR	FE_CO :93.8%@2.3 V	22 h@58 mA cm^-2	[181]	CoTPP@RGO-T	Co-based	ORR	50 mol h^-1 g cat^-1 @500 mA cm^-2	200 h @40 0mA cm^-2	[184]
CoN₄-Por- COF	Co-based	CO₂RR	—	—	[193]	PFC-72-Co	Co-based	ORR	0.68 V @FE_H2O2:> 90%	—	[197]
CoPCOP@ CNT	Co-based	NO_xRR	-0.8 V vs. RHE FE: 98%, -1.0 V vs. RHE, 5.34 mW cm^-2 FE > 90%	—	[59]	NiFe-TCPP	Ni/ Fe-based	OER	290.2 mV @1000 mA cm^-2	1000 h @500 mA cm^-2	[39]
CoPB--C8	Co-based	NO₃^-RR	FE_NH3 > 90% @1.04-1.54 V	—	[126]	FeTMA/CNTs	Fe-based	NO_xRR	-1.5 V vs. Ag/AgCl FE_NH3 > 90%	—	[65]
CoTMA/ CNTs	Co-based	NO₃^-RR	1.5 V @ FE_NH3: 94.7%	—	[190]	m-NiTPyP	Ni-based	OER, HER	10 mA cm^-2@267/138 mV	60 h @1.65 V	[107]
PBIPorCo/ 3D-G	Co-based	OER/ORR	OER 290 mV @10 mA cm^-2; ORR (E_1/2) 0.90 V vs. RHE	L-ZAB >200 h@356.8 mW^-2	[62]	Fe-porphyrin	Fe-based	NO₂RR	FE_NH3 :90% @1.09 V	—	[108]
Metal porphyrin 1-M (M = Co, Fe)	Co/Fe- based	OER	430 mV @10 mA cm^-2	—	[88]	TAPP-OFPc[Ni]-COF	Fe/ Ni-based	UOR	10mA cm^-2@1.37V	—	[109]
CoPc-DEG MDE@CC	Co-based	HER	—	25 h@1000 mA cm^-2	[68]	++N18C6-FeP	Fe-based	CO₂RR	FE_CO: 95% @2.25 V	—	[122]
guanidino- functionalized Fe-porphyrins	Fe-based	CO₂RR	FE_CO: 98% @ 2.1 V	—	[123]	CuPOF-Bpy/ Cu₂O@CNT	Cu-based	CO₂RR	FE_C2H4: 71% @1.1 V	16 h @1.1V	[158]
OPA-PCN-222(Fe)	Fe-based	NOR, NRR	FE: 70.7% @ 1.6 V	—	[125]	CuTphCOF- Dct	Cu-based	CO₂RR	FE_CH4: 68% @0.8 ~1.0 V	5 h @0.9V	[165]
Fe-TPPNH₂	Fe-based	CO₂RR	105 mA cm^-2@ 0.8 V	—	[162]	CuNCP	Cu-based	CO₂RR	-1.8 V @170 mA cm^-2	—	[219]
Zr-BDDB MOF	Fe-based	NO₃^- RR	0.5 V @FE_NH3:95.6%	24 h @ 0.5 V	[72]	NiTPP	Ni-based	CO₂RR	FE_CO: 98.3% @500 mA cm^-2	—	[116]
FeTCPP-NSs-BAA	Fe-based	CO₂RR	0.3 V@FE_C2H5OH: 89.2%	20 h @ 0.7 V	[204]	m-NiTPyP	Ni-based	OER、HER	10 mA cm^-2@267/138 mV	60 h @1.65 V	[107]
FeTCPP	Fe-based	CO₂RR	—	—	[174]	TPPNi	Ni-based	CO₂RR	FE_CO: 99.3% @1.10 V	—	[163]
PCN-222(Fe)	Fe-based	CO₂RR	—	—	[41]	Ni₅₀/ Zn₅₀-COF	Ni/ Zn-based	CO₂RR	0.6 V @CO₂RR FE_CO: 79%	—	[205]
o-Cu-Por-Sa(αβαβ)	Cu-based	CO₂RR	45.76 mA cm^-2@-0.8 V vs. RHE FE_CH4: 84%	—	[57]	Pt10/ Ni-ZrO₂-NC	Ni/ Pt-based	HER	57.5 mV @100 mA cm^-2	230 h @100 mA cm^-2	[210]
Cu-PMOF	Cu-based	NH₂CONH₂	25.5 μmol h^-1 mg_cat^-1@0.55 V	36 h @0.55 V	[136]	NiPc-azo- H₂Pp@CNTs	Ni-based	CO₂RR	1.48 V @370 mA cm^-2	24 h @200 mA cm^-2	[211]
Cu porphyrins to afford analogues 1-4	Cu-based	HER	—	—	[51]	Hg-MTPP	Hg-based	CO₂RR	FE_CO: 100% @1.2 A cm^-2	360 h @420 mA cm^-2	[152]
Cu-TMCPP/ CNT	Cu-based	CO₂RR	91.8 mA cm^-2 @1.08 V	9 h @ 1.08 V	[138]	In-TCPP	In-based	CO₂RR	FE_HCOOH >80% @25 mA cm^-2	50 h @25 mA cm^-2	[182]
Cu-PMOF	Cu-based	CO₂RR	337.5 mA cm^-2 @1.23 V	—	[140]

Table 1 Classification of types, performances and applications of porphyrin catalysts discussed in this review.

Porphyrin catalyst	Types of catalysts	Applications	Catalytic performance	Stability	Ref.	Porphyrin catalyst	Types of catalyst	Applications	Catalytic performance	Stability	Ref.
Cu₂O@Cu- TCPP(Co)	Cu/Co- based	CO₂RR	500 mA cm^-2 FE_C2H4: 54 ± 2% FE_C2+: 69 ± 4%	>20 h@300 mA cm^-2	[40]	Pt@Co- NPC-800	Co-based	HER	1.32 A cm^-2 @60 °C 2.34 V	22 h @1.9 V	[164]
DAE-BPy- CoPor	Co-based	CO₂RR	20.1 mA cm^-2@-1.0 V vs. RHE FE_CO : 90.5%	24 h@-0.9 V vs. RHE FE> 80%	[53]	CoT-sp2C-P- COF-COOH	Co-based	HER	0.75 V @57.49 mA cm^-2	—	[186]
Co-PPOLs	Co-based	CO₂RR	-0.9 V vs. RHE FE_CO > 94.2%	>20 h@200 mA cm^-2	[60]	Co-N₃C₁-COF	Co-based	4e^-ORR	η: 0.338 V E_1/2:0.794 V	—	[99]
Co-TQCOF	Co-based	CO₂RR	-1.0 V @-20 mA cm^-2 FE: 93.9%	12 h@FE>80%	[63]	Co-N_x	Co-based	2e^-ORR	FE_H2O2: 85% @500 mA cm^-2	12 h @50 mA cm^-2	[114]
CoPc/ppy/ GDE	Co-based	CO₂RR	—	—	[71]	1-CoZn	Zn/ Co-based	ORR	—	10h@0.44V	[146]
CoCoPCP/ CNT	Co-based	CO₂RR	FE_CO: 94% @0.44 V	24 h@0.55 V	[148]	CoPorF/CNT	Co-based	ORR	464 mA cm^-2@3.32 V	48 h @50mA cm^-2	[168]
EP-CoP/Cu	Co-based	CO₂RR	726 mA cm^-2@0.9 V	—	[161]	Co-TEPP-COP/rGO	Co-based	ORR	1.2V FE_H2O2 > 95%	30 h @50 mA cm^-2	[183]
Vg-Por(Co)-MOF	Co-based	CO₂RR	FE_CO :93.8%@2.3 V	22 h@58 mA cm^-2	[181]	CoTPP@RGO-T	Co-based	ORR	50 mol h^-1 g cat^-1 @500 mA cm^-2	200 h @40 0mA cm^-2	[184]
CoN₄-Por- COF	Co-based	CO₂RR	—	—	[193]	PFC-72-Co	Co-based	ORR	0.68 V @FE_H2O2:> 90%	—	[197]
CoPCOP@ CNT	Co-based	NO_xRR	-0.8 V vs. RHE FE: 98%, -1.0 V vs. RHE, 5.34 mW cm^-2 FE > 90%	—	[59]	NiFe-TCPP	Ni/ Fe-based	OER	290.2 mV @1000 mA cm^-2	1000 h @500 mA cm^-2	[39]
CoPB--C8	Co-based	NO₃^-RR	FE_NH3 > 90% @1.04-1.54 V	—	[126]	FeTMA/CNTs	Fe-based	NO_xRR	-1.5 V vs. Ag/AgCl FE_NH3 > 90%	—	[65]
CoTMA/ CNTs	Co-based	NO₃^-RR	1.5 V @ FE_NH3: 94.7%	—	[190]	m-NiTPyP	Ni-based	OER, HER	10 mA cm^-2@267/138 mV	60 h @1.65 V	[107]
PBIPorCo/ 3D-G	Co-based	OER/ORR	OER 290 mV @10 mA cm^-2; ORR (E_1/2) 0.90 V vs. RHE	L-ZAB >200 h@356.8 mW^-2	[62]	Fe-porphyrin	Fe-based	NO₂RR	FE_NH3 :90% @1.09 V	—	[108]
Metal porphyrin 1-M (M = Co, Fe)	Co/Fe- based	OER	430 mV @10 mA cm^-2	—	[88]	TAPP-OFPc[Ni]-COF	Fe/ Ni-based	UOR	10mA cm^-2@1.37V	—	[109]
CoPc-DEG MDE@CC	Co-based	HER	—	25 h@1000 mA cm^-2	[68]	++N18C6-FeP	Fe-based	CO₂RR	FE_CO: 95% @2.25 V	—	[122]
guanidino- functionalized Fe-porphyrins	Fe-based	CO₂RR	FE_CO: 98% @ 2.1 V	—	[123]	CuPOF-Bpy/ Cu₂O@CNT	Cu-based	CO₂RR	FE_C2H4: 71% @1.1 V	16 h @1.1V	[158]
OPA-PCN-222(Fe)	Fe-based	NOR, NRR	FE: 70.7% @ 1.6 V	—	[125]	CuTphCOF- Dct	Cu-based	CO₂RR	FE_CH4: 68% @0.8 ~1.0 V	5 h @0.9V	[165]
Fe-TPPNH₂	Fe-based	CO₂RR	105 mA cm^-2@ 0.8 V	—	[162]	CuNCP	Cu-based	CO₂RR	-1.8 V @170 mA cm^-2	—	[219]
Zr-BDDB MOF	Fe-based	NO₃^- RR	0.5 V @FE_NH3:95.6%	24 h @ 0.5 V	[72]	NiTPP	Ni-based	CO₂RR	FE_CO: 98.3% @500 mA cm^-2	—	[116]
FeTCPP-NSs-BAA	Fe-based	CO₂RR	0.3 V@FE_C2H5OH: 89.2%	20 h @ 0.7 V	[204]	m-NiTPyP	Ni-based	OER、HER	10 mA cm^-2@267/138 mV	60 h @1.65 V	[107]
FeTCPP	Fe-based	CO₂RR	—	—	[174]	TPPNi	Ni-based	CO₂RR	FE_CO: 99.3% @1.10 V	—	[163]
PCN-222(Fe)	Fe-based	CO₂RR	—	—	[41]	Ni₅₀/ Zn₅₀-COF	Ni/ Zn-based	CO₂RR	0.6 V @CO₂RR FE_CO: 79%	—	[205]
o-Cu-Por-Sa(αβαβ)	Cu-based	CO₂RR	45.76 mA cm^-2@-0.8 V vs. RHE FE_CH4: 84%	—	[57]	Pt10/ Ni-ZrO₂-NC	Ni/ Pt-based	HER	57.5 mV @100 mA cm^-2	230 h @100 mA cm^-2	[210]
Cu-PMOF	Cu-based	NH₂CONH₂	25.5 μmol h^-1 mg_cat^-1@0.55 V	36 h @0.55 V	[136]	NiPc-azo- H₂Pp@CNTs	Ni-based	CO₂RR	1.48 V @370 mA cm^-2	24 h @200 mA cm^-2	[211]
Cu porphyrins to afford analogues 1-4	Cu-based	HER	—	—	[51]	Hg-MTPP	Hg-based	CO₂RR	FE_CO: 100% @1.2 A cm^-2	360 h @420 mA cm^-2	[152]
Cu-TMCPP/ CNT	Cu-based	CO₂RR	91.8 mA cm^-2 @1.08 V	9 h @ 1.08 V	[138]	In-TCPP	In-based	CO₂RR	FE_HCOOH >80% @25 mA cm^-2	50 h @25 mA cm^-2	[182]
Cu-PMOF	Cu-based	CO₂RR	337.5 mA cm^-2 @1.23 V	—	[140]

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Multiscale optimization design of porphyrin electrocatalysts for redox reactions under operational conditions

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