在水分解技術中，涉及緩慢四電子轉移的氧氣析出反應（Oxygen evolution reaction, OER）為整體的速率決定步驟。而銥基材料在酸性環境展現優異的OER催化活性。然而，塊材的表面積有限，阻礙了其內部活性位點的充分利用。透過後修飾技術，能將銥活性位點引入具有水穩定性且高比表面積的鋯基金屬有機骨架（Metal–organic frameworks, MOFs）中。另外，鹵素原子能誘發電子結構重組，進而調節銥基催化劑的電子結構，達到加速反應動力學的效果。因此，我們利用不同鹵素官能基化或未官能基化的對苯二甲酸當作配體，合成一系列的UiO-66-X（X = Cl, Br, I, H），並透過後修飾將空間中分散的銥位點固定於這些UiO-66-X缺失配體缺陷的節點上。隨後於0.1 M HClO4中測試這些Ir-UiO-66-X的電催化性能。
交流阻抗實驗與弛豫時間分佈（Distribution of relaxation times, DRT）表示，鹵素官能基化配體能有效降低鄰近銥位點上OER速率決定步驟的反應動力學阻抗；然而，碘原子較大的半徑會阻塞孔道，使Ir-UiO-66-I在OER過程伴隨著巨大的質傳阻力。綜合上述，Ir-UiO-66-Cl同時具備高效質傳能力與快速的催化動力學，因而展現出最佳的OER電催化活性。

Oxygen evolution reaction (OER) is the rate-determining step in water electrolysis due to the sluggish four-electron transfer process. Therefore, the use of an electrocatalyst is necessary. And Iridium-based materials show excellent electrocatalytic OER activity in acidic electrolytes. Nevertheless, the limited surface area of bulk iridium-based materials hinders the utilization of internal active sites. Through post-synthetic modification, iridium active units can be incorporated within a metal–organic framework (MOF), UiO-66, enabling appealing performance for OER. Moreover, halogen atoms could cause an electronic reconfiguration and modulate the electronic structure of iridium-based electrocatalysts for accelerating the reaction kinetics process.
In this study, a series of UiO-66 analogues, UiO-66-X (X = Cl, Br, I, H), are synthesized via different halogen-functionalized or non-functionalized terephthalate linkers, and the spatially dispersed iridium catalytic sites are immobilized on the missing-linker defective nodes of these UiO-66-X. The electrocatalytic performance of the resulting iridium-functionalized UiO-66-X is probed in 0.1 M HClO4. Impedance experiments and further distribution of relaxation times (DRT) analysis suggest that all halogen-functionalized linkers reduce the resistance of the rate-determining OER step occurring on neighboring iridium sites, while Ir-UiO-66-I has a huge resistance for mass transfer during the OER. As a result, with both efficient mass transfer and fast catalytic kinetics, Ir-UiO-66-Cl exhibits the best electrocatalytic activity for the OER.

[1] L. Peng and Z. Wei. Catalyst engineering for electrochemical energy conversion from water to water: water electrolysis and the hydrogen fuel cell. Engineering, 6, 653-679, 2020.
[2] F. Mueller-Langer, E. Tzimas, M. Kaltschmitt, and S. Peteves. Techno-economic assessment of hydrogen production processes for the hydrogen economy for the short and medium term. International Journal of Hydrogen Energy, 32, 3797-3810, 2007.
[3] G. Weidong and Y. Zhuoyong. Research on non-grid-connected wind power/water-electrolytic hydrogen production system. International Journal of Hydrogen Energy, 37, 737-740, 2012.
[4] F. Ustolin, J. J. Lamb, O. S. Burheim, and B. G. Pollet. Energy and safety of hydrogen storage. Hydrogen, Biomass and Bioenergy, 133-153, 2020.
[5] N. Ismail, F. Qin, C. Fang, D. Liu, B. Liu, X. Liu, Z. l. Wu, Z. Chen, and W. Chen. Electrocatalytic acidic oxygen evolution reaction: From nanocrystals to single atoms. Aggregate, 2, e106, 2021.
[6] M. Fan, X. Liang, H. Chen, and X. Zou. Low-iridium electrocatalysts for acidic oxygen evolution. Dalton Transactions, 49, 15568-15573, 2020.
[7] L. Chen, W. Zhao, J. Zhang, M. Liu, Y. Jia, R. Wang, and M. Chai. Recent research on iridium‐based electrocatalysts for acidic oxygen evolution reaction from the origin of reaction mechanism. Small, 20, 2403845, 2024.
[8] H.-S. Oh, H. N. Nong, T. Reier, M. Gliech, and P. Strasser. Oxide-supported Ir nanodendrites with high activity and durability for the oxygen evolution reaction in acid PEM water electrolyzers. Chemical Science, 6, 3321-3328, 2015.
[9] T. Reier, H. N. Nong, D. Teschner, R. Schlögl, and P. Strasser. Electrocatalytic oxygen evolution reaction in acidic environments–reaction mechanisms and catalysts. Advanced Energy Materials, 7, 1601275, 2017.
[10] C. Wang, F. Yang, and L. Feng. Recent advances in iridium-based catalysts with different dimensions for the acidic oxygen evolution reaction. Nanoscale Horizons, 8, 1174-1193, 2023.
[11] A. R. Harris, D. B. Grayden, and S. E. John. Electrochemistry in a two-or three-electrode configuration to understand monopolar or bipolar configurations of platinum bionic implants. Micromachines, 14, 722, 2023.
[12] D. J. Martin, B. D. McCarthy, E. S. Rountree, and J. L. Dempsey. Qualitative extension of the EC′ Zone Diagram to a molecular catalyst for a multi-electron, multi-substrate electrochemical reaction. Dalton Transactions, 45, 9970-9976, 2016.
[13] C. Sandford, M. A. Edwards, K. J. Klunder, D. P. Hickey, M. Li, K. Barman, M. S. Sigman, H. S. White, and S. D. Minteer. A synthetic chemist's guide to electroanalytical tools for studying reaction mechanisms. Chemical Science, 10, 6404-6422, 2019.
[14] J. Zhang, X. Cao, Y.-F. Jiang, S.-F. Hung, W. Liu, H. B. Yang, C.-Q. Xu, D.-S. Li, T. Zhang, and Y. Li. Surface enrichment of Ir on the IrRu alloy for efficient and stable water oxidation catalysis in acid. Chemical Science, 13, 12114-12121, 2022.
[15] K. Klyukin, A. Zagalskaya, and V. Alexandrov. Role of dissolution intermediates in promoting oxygen evolution reaction at RuO2 (110) surface. The Journal of Physical Chemistry C, 123, 22151-22157, 2019.
[16] N. Danilovic, R. Subbaraman, K.-C. Chang, S. H. Chang, Y. J. Kang, J. Snyder, A. P. Paulikas, D. Strmcnik, Y.-T. Kim, and D. Myers. Activity–stability trends for the oxygen evolution reaction on monometallic oxides in acidic environments. The Journal of Physical Chemistry Letters, 5, 2474-2478, 2014.
[17] W. Li, Y. Bu, X. Ge, F. Li, G. F. Han, and J. B. Baek. Recent advances in iridium‐based electrocatalysts for acidic electrolyte oxidation. ChemSusChem, 17, e202400295, 2024.
[18] I. C. Man, H. Y. Su, F. Calle‐Vallejo, H. A. Hansen, J. I. Martínez, N. G. Inoglu, J. Kitchin, T. F. Jaramillo, J. K. Nørskov, and J. Rossmeisl. Universality in oxygen evolution electrocatalysis on oxide surfaces. ChemCatChem, 3, 1159-1165, 2011.
[19] D.-Y. Kuo, H. Paik, J. Kloppenburg, B. Faeth, K. M. Shen, D. G. Schlom, G. Hautier, and J. Suntivich. Measurements of oxygen electroadsorption energies and oxygen evolution reaction on RuO2 (110): a discussion of the Sabatier principle and its role in electrocatalysis. Journal of the American Chemical Society, 140, 17597-17605, 2018.
[20] D.-Y. Kuo, J. K. Kawasaki, J. N. Nelson, J. Kloppenburg, G. Hautier, K. M. Shen, D. G. Schlom, and J. Suntivich. Influence of surface adsorption on the oxygen evolution reaction on IrO2 (110). Journal of the American Chemical Society, 139, 3473-3479, 2017.
[21] M. Zlatar, D. Escalera-Lopez, C. Simon, V. Briega-Martos, K. Stojanovski, and S. Cherevko. pH dependence of noble metals dissolution: Iridium. Electrochimica Acta, 513, 145450, 2025.
[22] Y. Lee, J. Suntivich, K. J. May, E. E. Perry, and Y. Shao-Horn. Synthesis and activities of rutile IrO2 and RuO2 nanoparticles for oxygen evolution in acid and alkaline solutions. The Journal of Physical Chemistry Letters, 3, 399-404, 2012.
[23] Z. Shi, X. Wang, J. Ge, C. Liu, and W. Xing. Fundamental understanding of the acidic oxygen evolution reaction: mechanism study and state-of-the-art catalysts. Nanoscale, 12, 13249-13275, 2020.
[24] J. T. Mefford, X. Rong, A. M. Abakumov, W. G. Hardin, S. Dai, A. M. Kolpak, K. P. Johnston, and K. J. Stevenson. Water electrolysis on La1− xSr xCoO3−δ perovskite electrocatalysts. Nature Communications, 7, 11053, 2016.
[25] A. Lončar, D. Escalera‐López, S. Cherevko, and N. Hodnik. Inter‐relationships between oxygen evolution and iridium dissolution mechanisms. Angewandte Chemie International Edition, 61, e202114437, 2022.
[26] E. Fabbri and T. J. Schmidt. Oxygen evolution reaction—the enigma in water electrolysis. ACS Catalysis, 8, 9765-9774, 2018.
[27] W. Li, J. Zhang, C. Yang, Z. Geng, X. Chen, Q. Liu, B. Wang, and L. Wang. Modulating iridium coordination to control the oxygen evolution reaction pathway. Journal of the American Chemical Society, 147, 40697-40707, 2025.
[28] T. E. Chang, C. H. Chuang, Y. H. Chen, Y. C. Wang, Y. J. Gu, and C. W. Kung. Iridium‐Functionalized Metal‐Organic Framework Nanocrystals Interconnected by Carbon Nanotubes Competent for Electrocatalytic Water Oxidation. ChemCatChem, 14, e202200199, 2022.
[29] N. Diklic, A. H. Clark, J. Herranz, D. Aegerter, J. S. Diercks, A. Beard, V. A. Saveleva, P. Chauhan, M. Nachtegaal, and T. Huthwelker. Surface Ir+5 formation as a universal prerequisite for O2 evolution on Ir oxides. ACS Catalysis, 13, 11069-11079, 2023.
[30] H. Furukawa, K. E. Cordova, M. O’Keeffe, and O. M. Yaghi. The chemistry and applications of metal-organic frameworks. Science, 341, 1230444, 2013.
[31] S. Kitagawa, R. Kitaura, and S. i. Noro. Functional porous coordination polymers. Angewandte Chemie International Edition, 43, 2334-2375, 2004.
[32] K. Sumida, D. L. Rogow, J. A. Mason, T. M. McDonald, E. D. Bloch, Z. R. Herm, T.-H. Bae, and J. R. Long. Carbon dioxide capture in metal–organic frameworks. Chemical Reviews, 112, 724-781, 2012.
[33] N. Song, R. Huai, Y. Zhao, L. Yang, D. Zhang, and Z. Zhou. Luminescent metal–organic frameworks as optical sensors for selective sensing towards Fe3+ and Cu2+. CrystEngComm, 26, 577-593, 2024.
[34] T. Chen and D. Zhao. Post-synthetic modification of metal-organic framework-based membranes for enhanced molecular separations. Coordination Chemistry Reviews, 491, 215259, 2023.
[35] S. M. Cohen. Postsynthetic methods for the functionalization of metal–organic frameworks. Chemical Reviews, 112, 970-1000, 2012.
[36] T. Luo, L. Gilmanova, and S. Kaskel. Advances of MOFs and COFs for photocatalytic CO2 reduction, H2 evolution and organic redox transformations. Coordination Chemistry Reviews, 490, 215210, 2023.
[37] J. Y. Choi, B. Check, X. Fang, S. Blum, H. T. Pham, K. Tayman, and J. Park. Photocatalytic hydrogen peroxide production through functionalized semiconductive metal–organic frameworks. Journal of the American Chemical Society, 146, 11319-11327, 2024.
[38] A. J. Young, R. Guillet-Nicolas, E. S. Marshall, F. Kleitz, A. J. Goodhand, L. B. Glanville, M. R. Reithofer, and J. M. Chin. Direct ink writing of catalytically active UiO-66 polymer composites. Chemical Communications, 55, 2190-2193, 2019.
[39] M. Kim, J. Jeong, D. H. Kim, G. Park, J. Yi, S. Kim, H. Kim, C. H. Choi, H. Shin, and S. S. Park. Tailoring Electrochemical Water Oxidation Activity From the Isostructural Series of Alkaline‐Stable Bimetallic Fe, Ni‐Azolate Metal–Organic Frameworks. Advanced Energy Materials, 14, 2401198, 2024.
[40] N. C. Burtch, H. Jasuja, and K. S. Walton. Water stability and adsorption in metal–organic frameworks. Chemical Reviews, 114, 10575-10612, 2014.
[41] A. J. Howarth, Y. Liu, P. Li, Z. Li, T. C. Wang, J. T. Hupp, and O. K. Farha. Chemical, thermal and mechanical stabilities of metal–organic frameworks. Nature Reviews Materials, 1, 1-15, 2016.
[42] W. Zheng and L. Y. S. Lee. Metal–organic frameworks for electrocatalysis: catalyst or precatalyst? ACS Energy Letters, 6, 2838-2843, 2021.
[43] S. Yuan, L. Feng, K. Wang, J. Pang, M. Bosch, C. Lollar, Y. Sun, J. Qin, X. Yang, and P. Zhang. Stable metal–organic frameworks: design, synthesis, and applications. Advanced Materials, 30, 1704303, 2018.
[44] S. Daliran, A. R. Oveisi, C.-W. Kung, U. Sen, A. Dhakshinamoorthy, C.-H. Chuang, M. Khajeh, M. Erkartal, and J. T. Hupp. Defect-enabling zirconium-based metal–organic frameworks for energy and environmental remediation applications. Chemical Society Reviews, 53, 6244-6294, 2024.
[45] I. Hod, P. Deria, W. Bury, J. E. Mondloch, C.-W. Kung, M. So, M. D. Sampson, A. W. Peters, C. P. Kubiak, and O. K. Farha. A porous proton-relaying metal-organic framework material that accelerates electrochemical hydrogen evolution. Nature Communications, 6, 8304, 2015.
[46] Y. Zhao, S. Zhang, M. Wang, J. Han, H. Wang, Z. Li, and X. Liu. Engineering iridium-based metal organic frameworks towards electrocatalytic water oxidation. Dalton Transactions, 47, 4646-4652, 2018.
[47] I. Hod, M. D. Sampson, P. Deria, C. P. Kubiak, O. K. Farha, and J. T. Hupp. Fe-porphyrin-based metal–organic framework films as high-surface concentration, heterogeneous catalysts for electrochemical reduction of CO2. ACS Catalysis, 5, 6302-6309, 2015.
[48] Y.-S. Tsai, S.-C. Yang, T.-H. Yang, C.-H. Wu, T.-C. Lin, and C.-W. Kung. Sulfonate-functionalized metal–organic framework as a porous “proton reservoir” for boosting electrochemical reduction of nitrate to ammonia. ACS Applied Materials & Interfaces, 16, 62185-62194, 2024.
[49] J. H. Cavka, S. Jakobsen, U. Olsbye, N. Guillou, C. Lamberti, S. Bordiga, and K. P. Lillerud. A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability. Journal of the American Chemical Society, 130, 13850-13851, 2008.
[50] M. R. DeStefano, T. Islamoglu, S. J. Garibay, J. T. Hupp, and O. K. Farha. Room-temperature synthesis of UiO-66 and thermal modulation of densities of defect sites. Chemistry of Materials, 29, 1357-1361, 2017.
[51] C.-W. Kung, S. Goswami, I. Hod, T. C. Wang, J. Duan, O. K. Farha, and J. T. Hupp. Charge transport in zirconium-based metal–organic frameworks. Accounts of Chemical Research, 53, 1187-1195, 2020.
[52] S. Lin, P. M. Usov, and A. J. Morris. The role of redox hopping in metal–organic framework electrocatalysis. Chemical Communications, 54, 6965-6974, 2018.
[53] K. Maindan, X. Li, J. Yu, and P. Deria. Controlling charge-transport in metal–organic frameworks: contribution of topological and spin-state variation on the iron–porphyrin centered redox hopping rate. The Journal of Physical Chemistry B, 123, 8814-8822, 2019.
[54] X. Li, S. Surendran Rajasree, V. Gude, K. Maindan, and P. Deria. Decoupling redox hopping and catalysis in metal‐organic frameworks‐based electrocatalytic CO2 reduction. Angewandte Chemie International Edition, 62, e202219046, 2023.
[55] S. Ahn, N. E. Thornburg, Z. Li, T. C. Wang, L. C. Gallington, K. W. Chapman, J. M. Notestein, J. T. Hupp, and O. K. Farha. Stable metal–organic framework-supported niobium catalysts. Inorganic Chemistry, 55, 11954-11961, 2016.
[56] H. Noh, Y. Cui, A. W. Peters, D. R. Pahls, M. A. Ortuño, N. A. Vermeulen, C. J. Cramer, L. Gagliardi, J. T. Hupp, and O. K. Farha. An exceptionally stable metal–organic framework supported molybdenum (VI) oxide catalyst for cyclohexene epoxidation. Journal of the American Chemical Society, 138, 14720-14726, 2016.
[57] C.-H. Chuang, J.-H. Li, Y.-C. Chen, Y.-S. Wang, and C.-W. Kung. Redox-hopping and electrochemical behaviors of metal–organic framework thin films fabricated by various approaches. The Journal of Physical Chemistry C, 124, 20854-20863, 2020.
[58] T.-E. Chang, C.-H. Chuang, and C.-W. Kung. An iridium-decorated metal–organic framework for electrocatalytic oxidation of nitrite. Electrochemistry Communications, 122, 106899, 2021.
[59] S. Yuan, J.-S. Qin, C. T. Lollar, and H.-C. Zhou. Stable metal–organic frameworks with group 4 metals: current status and trends. ACS Central Science, 4, 440-450, 2018.
[60] H. Song, J. Yu, Z. Tang, B. Yang, and S. Lu. Halogen‐doped carbon dots on amorphous cobalt phosphide as robust electrocatalysts for overall water splitting. Advanced Energy Materials, 12, 2102573, 2022.
[61] J. N. Lu, J. Liu, L. Z. Dong, S. L. Li, Y. H. Kan, and Y. Q. Lan. Exploring the influence of halogen coordination effect of stable bimetallic MOFs on oxygen evolution reaction. Chemistry–A European Journal, 25, 15830-15836, 2019.
[62] Q. Qi, Y. Zhang, C. Zhang, F. Liu, R. Liu, and J. Hu. Halogen-modified iron-based metal–organic frameworks for remarkably improved electrocatalytic oxygen evolution. The Journal of Physical Chemistry C, 128, 1936-1945, 2024.
[63] Y. Hu, Y. Fan, L. Li, J. Zhou, Z. Hu, J. Q. Wang, J. Dong, S. Zhao, and L. Zhang. Modulating 3d charge state via halogen ions in neighboring molecules of metal–organic frameworks for improving water oxidation. Small, 20, 2400042, 2024.
[64] D. O. Miles, D. Jiang, A. D. Burrows, J. E. Halls, and F. Marken. Conformal transformation of [Co(bdc)(DMF)] (Co-MOF-71, bdc= 1, 4-benzenedicarboxylate, DMF= N, N-dimethylformamide) into porous electrochemically active cobalt hydroxide. Electrochemistry Communications, 27, 9-13, 2013.
[65] W. Zheng, M. Liu, and L. Y. S. Lee. Electrochemical instability of metal–organic frameworks: in situ spectroelectrochemical investigation of the real active sites. ACS Catalysis, 10, 81-92, 2019.
[66] M. Meng, Y. Liu, Y. Shan, Y. Song, J. Li, Y. Shao, and L. Liu. Asymmetric distortion of orbital hybridization at halogen-doped IrO2 monolayers for acidic water electrolysis. Surface Science, 748, 122542, 2024.
[67] M. Kandiah, M. H. Nilsen, S. Usseglio, S. Jakobsen, U. Olsbye, M. Tilset, C. Larabi, E. A. Quadrelli, F. Bonino, and K. P. Lillerud. Synthesis and stability of tagged UiO-66 Zr-MOFs. Chemistry of Materials, 22, 6632-6640, 2010.
[68] M. Kalaj, M. R. Momeni, K. C. Bentz, K. S. Barcus, J. M. Palomba, F. Paesani, and S. M. Cohen. Halogen bonding in UiO-66 frameworks promotes superior chemical warfare agent simulant degradation. Chemical Communications, 55, 3481-3484, 2019.
[69] X. Duan, Q. Sha, P. Li, T. Li, G. Yang, W. Liu, E. Yu, D. Zhou, J. Fang, and W. Chen. Dynamic chloride ion adsorption on single iridium atom boosts seawater oxidation catalysis. Nature Communications, 15, 1973, 2024.
[70] S. Wannakao, T. Maihom, K. Kongpatpanich, J. Limtrakul, and V. Promarak. Halogen substitutions leading to enhanced oxygen evolution and oxygen reduction reactions in metalloporphyrin frameworks. Physical Chemistry Chemical Physics, 19, 29540-29548, 2017.
[71] R. C. Klet, Y. Liu, T. C. Wang, J. T. Hupp, and O. K. Farha. Evaluation of Brønsted acidity and proton topology in Zr-and Hf-based metal–organic frameworks using potentiometric acid–base titration. Journal of Materials Chemistry A, 4, 1479-1485, 2016.
[72] Y.-N. Chang, C.-H. Shen, C.-W. Huang, M.-D. Tsai, and C.-W. Kung. Defective metal–organic framework nanocrystals as signal amplifiers for electrochemical dopamine sensing. ACS Applied Nano Materials, 6, 3675-3684, 2023.
[73] W. Zheng. iR compensation for electrocatalysis studies: considerations and recommendations. ACS Energy Letters, 8, 1952-1958, 2023.
[74] U. Ruschewitz. Does fluorine make a difference? How Fluoro groups influence the (structural) properties of MOFs. European Journal of Inorganic Chemistry, 28, e202400809, 2025.
[75] S. Øien, D. Wragg, H. Reinsch, S. Svelle, S. Bordiga, C. Lamberti, and K. P. Lillerud. Detailed structure analysis of atomic positions and defects in zirconium metal–organic frameworks. Crystal Growth & Design, 14, 5370-5372, 2014.
[76] A. K. Zak, W. A. Majid, M. E. Abrishami, and R. Yousefi. X-ray analysis of ZnO nanoparticles by Williamson–Hall and size–strain plot methods. Solid State Sciences, 13, 251-256, 2011.
[77] C.-H. Shen, Y.-N. Chang, Y.-L. Chen, and C.-W. Kung. Sulfonate-grafted metal–organic framework─ a porous alternative to Nafion for electrochemical sensors. ACS Materials Letters, 5, 1938-1943, 2023.
[78] M. Kandiah, S. Usseglio, S. Svelle, U. Olsbye, K. P. Lillerud, and M. Tilset. Post-synthetic modification of the metal–organic framework compound UiO-66. Journal of Materials Chemistry, 20, 9848-9851, 2010.
[79] Y. Han, M. Liu, K. Li, Y. Zuo, Y. Wei, S. Xu, G. Zhang, C. Song, Z. Zhang, and X. Guo. Facile synthesis of morphology and size-controlled zirconium metal–organic framework UiO-66: the role of hydrofluoric acid in crystallization. CrystEngComm, 17, 6434-6440, 2015.
[80] S. Trasatti and O. Petrii. Real surface area measurements in electrochemistry. Pure and Applied Chemistry, 63, 711-734, 1991.
[81] G. K. Wertheim and H. J. Guggenheim. Conduction-electron screening in metallic oxides: IrO2. Physical Review B, 22, 4680, 1980.
[82] R.-S. Chen, A. Korotcov, Y.-S. Huang, and D.-S. Tsai. One-dimensional conductive IrO2 nanocrystals. Nanotechnology, 17, R67-R87, 2006.
[83] D. Escalera-López, S. Czioska, J. Geppert, A. Boubnov, P. Röse, E. Saraci, U. Krewer, J.-D. Grunwaldt, and S. Cherevko. Phase-and surface composition-dependent electrochemical stability of Ir-Ru nanoparticles during oxygen evolution reaction. ACS Catalysis, 11, 9300-9316, 2021.
[84] S. Lin, Y. Pineda‐Galvan, W. A. Maza, C. C. Epley, J. Zhu, M. C. Kessinger, Y. Pushkar, and A. J. Morris. Electrochemical water oxidation by a catalyst‐modified metal–organic framework thin film. ChemSusChem, 10, 514-522, 2017.
[85] L. R. Faulkner and A. J. Bard. Electrochemical methods: fundamentals and applications. Wiley, 2000.
[86] J. Bisquert, G. Garcia-Belmonte, P. Bueno, E. Longo, and L. Bulhões. Impedance of constant phase element (CPE)-blocked diffusion in film electrodes. Journal of Electroanalytical Chemistry, 452, 229-234, 1998.
[87] A. Minguzzi, F.-R. F. Fan, A. Vertova, S. Rondinini, and A. J. Bard. Dynamic potential–pH diagrams application to electrocatalysts for water oxidation. Chemical Science, 3, 217-229, 2012.
[88] F. Dion and A. Lasia. The use of regularization methods in the deconvolution of underlying distributions in electrochemical processes. Journal of Electroanalytical Chemistry, 475, 28-37, 1999.
[89] H. Qu, J. Kafle, J. Harris, D. Zheng, J. Koshina, D. Boone, A. M. Drake, C. J. Abegglen, and D. Qu. Application of ac impedance as diagnostic tool–Low temperature electrolyte for a Li-ion battery. Electrochimica Acta, 322, 134755, 2019.
[90] A. Oz, S. Hershkovitz, N. Belman, E. Tal-Gutelmacher, and Y. Tsur. Analysis of impedance spectroscopy of aqueous supercapacitors by evolutionary programming: finding DFRT from complex capacitance. Solid State Ionics, 288, 311-314, 2016.
[91] C.-H. Shen, Y. Zhao, H. N. Nam, L. Zhu, Q. M. Phung, V. Austen, M. Kim, D. Jiang, X. Wei, and T. Yokoshima. Unlocking coordination sites of metal–organic frameworks for high-density and accessible copper nanoparticles toward electrochemical nitrate reduction to ammonia. Chemical Science, 16, 7026-7038, 2025.
[92] T. H. Wan, M. Saccoccio, C. Chen, and F. Ciucci. Influence of the discretization methods on the distribution of relaxation times deconvolution: implementing radial basis functions with DRT tools. Electrochimica Acta, 184, 483-499, 2015.
[93] A.-L. Chan, H. Yu, K. S. Reeves, and S. M. Alia. Identifying electrochemical processes by distribution of relaxation times in proton exchange membrane electrolyzers. Journal of Power Sources, 628, 235850, 2025.
[94] Y. Li, Y. Jiang, J. Dang, X. Deng, B. Liu, J. Ma, F. Yang, M. Ouyang, and X. Shen. Application of distribution of relaxation times method in polymer electrolyte membrane water electrolyzer. Chemical Engineering Journal, 451, 138327, 2023.
[95] P. K. Giesbrecht and M. S. Freund. Investigation of water oxidation at IrO2 electrodes in nafion-based membrane electrode assemblies using impedance spectroscopy and distribution of relaxation times analysis. The Journal of Physical Chemistry C, 126, 17844-17861, 2022.
[96] M. Blasco-Ahicart, J. Soriano-López, J. J. Carbó, J. M. Poblet, and J.-R. Galan-Mascaros. Polyoxometalate electrocatalysts based on earth-abundant metals for efficient water oxidation in acidic media. Nature Chemistry, 10, 24-30, 2018.
[97] Y. Dong, S. Komarneni, N. Wang, W. Hu, and W. Huang. An in situ anion exchange induced high-performance oxygen evolution reaction catalyst for the pH-near-neutral potassium borate electrolyte. Journal of Materials Chemistry A, 7, 6995-7005, 2019.
[98] I. Roger and M. D. Symes. Efficient electrocatalytic water oxidation at neutral and high pH by adventitious nickel at nanomolar concentrations. Journal of the American Chemical Society, 137, 13980-13988, 2015.
[99] M. Dincă, Y. Surendranath, and D. G. Nocera. Nickel-borate oxygen-evolving catalyst that functions under benign conditions. Proceedings of the National Academy of Sciences, 107, 10337-10341, 2010.
[100] C.-W. Kung, J. E. Mondloch, T. C. Wang, W. Bury, W. Hoffeditz, B. M. Klahr, R. C. Klet, M. J. Pellin, O. K. Farha, and J. T. Hupp. Metal–organic framework thin films as platforms for atomic layer deposition of cobalt ions to enable electrocatalytic water oxidation. ACS Applied Materials & Interfaces, 7, 28223-28230, 2015.