Abstract
Ruthenium-based catalyst is one of the most active catalysts for oxygen evolution reaction (OER) in acid media. However, the strong bonding between the Ru sites and oxygen intermediates leads to high overpotential to trigger the OER process. Hence, pyrochlore rare-earth ruthenate (RE2-Ru2O7) structures with a series of rare-earth elements (Nd, Sm, Gd, Er, and Yb) were constructed to tune the electronic structure of the Ru sites. Surface structure analysis indicated that the increase of the radius of the rare-earth cations resulted in higher content of defective oxygen (the percentage of the defective oxygen increased from 29.5% to 49.7%) in the RE2Ru2O7 structure due to the weakened hybridization of the Ru-O bond. This reduced the valence states of the Ru sites and enlarged the gap between the 4d band center and the Fermi level (EF) of Ru, resulting in the weakened adsorption of oxygen intermediates and the improved OER performance in acid media. Among the as-prepared ruthenium pyrochlores, Nd2Ru2O7 displayed the lowest OER onset overpotential (210 mV) and Tafel slope (58.48 mV dec−1), as well as 30 times higher intrinsic activity and much higher durability than the state-of-art RuO2 catalyst.
摘要
钌(Ru)基催化剂是酸性介质中析氧反应(OER)最为活泼的催 化剂之一. 然而, Ru活性位点与含氧中间产物之间的强键合导致析 氧反应过电势较高. 本文, 利用一系列稀土元素(Nd、Sm、Gd、Er 和Yb)构建了烧绿石型稀土钌酸盐(RE2Ru2O7)结构来调整Ru位点 的电子结构. 表面结构分析表明, 由于Ru–O键杂化减弱, 随着稀土 离子半径的增大, RE2Ru2O7结构中缺陷氧含量增加(缺陷氧的比例 从29.5%增加到49.7%). 降低了的Ru的价态, 扩大了Ru的4d能带中 心与费米能级(EF)之间的间隙, 从而削弱了对氧中间体的吸附, 提 高了酸性介质中的OER性能. 在所制备的钌烧绿石中, Nd2Ru2O7表 现出最低的O E R 起始过电势(2 1 0 m V) 和T a f e l 斜率 (58.48 mV dec−1), 并且比最先进的RuO2催化剂具有高30倍的固有 活性和更好的耐久性.
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References
Man IC, Su H, CalleVallejo F, et al. Universality in oxygen evolution electrocatalysis on oxide surfaces. ChemCatChem, 2011, 3: 1159–1165
Seh ZW, Kibsgaard J, Dickens CF, et al. Combining theory and experiment in electrocatalysis: Insights into materials design. Science, 2017, 355: eaad4998
Ni B, Zhang Q, Ouyang C, et al. The synthesis of sub-nano-thick Pd nanobelt-based materials for enhanced hydrogen evolution reaction activity. CCS Chem, 2020, 2: 642–654
Lin H, Sun B, Wang H, et al. Unique 1D Cd1−xZnxS@O-MoS2/NiOx nanohybrids: Highly efficient visible-light-driven photocatalytic hydrogen evolution via integrated structural regulation. Small, 2019, 15: 1804115
Zhang S, Lv F, Zhang X, et al. Ni@RuM (M=Ni or Co) core@shell nanocrystals with high mass activity for overall water-splitting catalysis. Sci China Mater, 2019, 62: 1868–1876
Zhuang G, Chen Y, Zhuang Z, et al. Oxygen vacancies in metal oxides: recent progress towards advanced catalyst design. Sci China Mater, 2020, 63: 2089–2118
Lee Y, Suntivich J, May KJ, et al. Synthesis and activities of rutile IrO2 and RuO2 nanoparticles for oxygen evolution in acid and alkaline solutions. J Phys Chem Lett, 2012, 3: 399–404
Nong HN, Oh HS, Reier T, et al. Oxide-supported IrNiOx core-shell particles as efficient, cost-effective, and stable catalysts for electrochemical water splitting. Angew Chem Int Ed, 2015, 54: 2975–2979
McCrory CCL, Jung S, Ferrer IM, et al. Benchmarking hydrogen evolving reaction and oxygen evolving reaction electrocatalysts for solar water splitting devices. J Am Chem Soc, 2015, 137: 4347–4357
Shang C, Cao C, Yu D, et al. Electron correlations engineer catalytic activity of pyrochlore iridates for acidic water oxidation. Adv Mater, 2018, 30: 1805104
Zhou D, Wang S, Jia Y, et al. NiFe hydroxide lattice tensile strain: enhancement of adsorption of oxygenated intermediates for efficient water oxidation catalysis. Angew Chem Int Ed, 2019, 58: 736–740
Zhang T, Liao SA, Dai LX, et al. Ir-Pd nanoalloys with enhanced surface-microstructure-sensitive catalytic activity for oxygen evolution reaction in acidic and alkaline media. Sci China Mater, 2018, 61: 926–938
Dickens CF, Montoya JH, Kulkarni AR, et al. An electronic structure descriptor for oxygen reactivity at metal and metal-oxide surfaces. Surf Sci, 2019, 681: 122–129
Shan J, Ling T, Davey K, et al. Transition-metal-doped RuIr bifunctional nanocrystals for overall water splitting in acidic environments. Adv Mater, 2019, 31: 1900510
Tian Y, Wang S, Velasco E, et al. A Co-doped nanorod-like RuO2 electrocatalyst with abundant oxygen vacancies for acidic water oxidation. iScience, 2020, 23: 100756
Yao Y, Hu S, Chen W, et al. Engineering the electronic structure of single atom Ru sites via compressive strain boosts acidic water oxidation electrocatalysis. Nat Catal, 2019, 2: 304–313
Cui X, Ren P, Ma C, et al. Robust interface Ru centers for highperformance acidic oxygen evolution. Adv Mater, 2020, 32: 1908126
Su J, Ge R, Jiang K, et al. Assembling ultrasmall copper-doped ruthenium oxide nanocrystals into hollow porous polyhedra: Highly robust electrocatalysts for oxygen evolution in acidic media. Adv Mater, 2018, 30: 1801351
Shan J, Raziq F, Humayun M, et al. Improved charge separation and surface activation via boron-doped layered polyhedron SrTiO3 for co-catalyst free photocatalytic CO2 conversion. Appl Catal B-Environ, 2017, 219: 10–17
Shen J, Li Y, Zhao H, et al. Modulating the photoelectrons of g-C3N4via coupling MgTi2O5 as appropriate platform for visible-light-driven photocatalytic solar energy conversion. Nano Res, 2019, 12: 1931–1936
Retuerto M, Calle-Vallejo F, Pascual L, et al. La1.5Sr0.5NiMn0.5-Ru0.5O6 double perovskite with enhanced ORR/OER bifunctional catalytic activity. ACS Appl Mater Interfaces, 2019, 11: 21454–21464
Miao X, Zhang L, Wu L, et al. Quadruple perovskite ruthenate as a highly efficient catalyst for acidic water oxidation. Nat Commun, 2019, 10: 3809
Kim J, Shih PC, Tsao KC, et al. High-performance pyrochlore-type yttrium ruthenate electrocatalyst for oxygen evolution reaction in acidic media. J Am Chem Soc, 2017, 139: 12076–12083
Sun W, Liu JY, Gong XQ, et al. OER activity manipulated by IrO6 coordination geometry: an insight from pyrochlore iridates. Sci Rep, 2016, 6: 38429
Parrondo J, George M, Capuano C, et al. Pyrochlore electrocatalysts for efficient alkaline water electrolysis. J Mater Chem A, 2015, 3: 10819–10828
Chen J, Shao Y, Li D. An antimonate pyrochlore (H1.23Sr0.45SbO3.48) for photocatalytic oxidation of benzene: effective oxygen usage and excellent activity. J Mater Chem A, 2017, 5: 937–941
Ji S, Qu Y, Wang T, et al. Rare-earth single erbium atoms for enhanced photocatalytic CO2 reduction. Angew Chem Int Ed, 2020, 59: 10651–10657
Xu H, Yu W, Pan K, et al. Confinement and antenna effect for ultrasmall Y2O3:Eu3+ nanocrystals supported by MOF with enhanced near-UV light absorption thereby enhanced luminescence and excellently multifunctional applications. Nano Res, 2021, 14: 720–729
Li P, Duan X, Kuang Y, et al. Tuning electronic structure of NiFe layered double hydroxides with vanadium doping toward high efficient electrocatalytic water oxidation. Adv Energy Mater, 2018, 8: 1703341
Lebedev D, Povia M, Waltar K, et al. Highly active and stable iridium pyrochlores for oxygen evolution reaction. Chem Mater, 2017, 29: 5182–5191
Teng Z, Zhu L, Tan Y, et al. Synthesis and structures of high-entropy pyrochlore oxides. J Eur Ceramic Soc, 2020, 40: 1639–1643
Du CF, Sun X, Yu H, et al. Synergy of Nb doping and surface alloy enhanced on water-alkali electrocatalytic hydrogen generation performance in Ti-based MXene. Adv Sci, 2019, 6: 1900116
Chen J, Cui P, Zhao G, et al. Low-coordinate iridium oxide confined on graphitic carbon nitride for highly efficient oxygen evolution. Angew Chem Int Ed, 2019, 58: 12540–12544
Lv F, Feng J, Wang K, et al. Iridium-tungsten alloy nanodendrites as pH-universal water-splitting electrocatalysts. ACS Cent Sci, 2018, 4: 1244–1252
Chen S, Huang H, Jiang P, et al. Mn-doped RuO2 nanocrystals as highly active electrocatalysts for enhanced oxygen evolution in acidic media. ACS Catal, 2019, 10: 1152–1160
Tackett BM, Sheng W, Kattel S, et al. Reducing iridium loading in oxygen evolution reaction electrocatalysts using core-shell particles with nitride cores. ACS Catal, 2018, 8: 2615–2621
Hu Y, Luo X, Wu G, et al. Engineering the atomic layer of RuO2 on PdO nanosheets boosts oxygen evolution catalysis. ACS Appl Mater Interfaces, 2019, 11: 42298–42304
Hao S, Wang Y, Zheng G, et al. Tuning electronic correlations of ultra-small IrO2 nanoparticles with La and Pt for enhanced oxygen evolution performance and long-durable stability in acidic media. Appl Catal B-Environ, 2020, 266: 118643
Xu J, Lian Z, Wei B, et al. Strong electronic coupling between ultrafine iridium-ruthenium nanoclusters and conductive, acid-stable tellurium nanoparticle support for efficient and durable oxygen evolution in acidic and neutral media. ACS Catal, 2020, 10: 3571–3579
Lin Y, Tian Z, Zhang L, et al. Chromium-ruthenium oxide solid solution electrocatalyst for highly efficient oxygen evolution reaction in acidic media. Nat Commun, 2019, 10: 162
Gao J, Xu CQ, Hung SF, et al. Breaking long-range order in iridium oxide by alkali ion for efficient water oxidation. J Am Chem Soc, 2019, 141: 3014–3023
Sanders MB, Krizan JW, Cava RJ. RE3Sb3Zn2O14 (RE = La, Pr, Nd, Sm, Eu, Gd): a new family of pyrochlore derivatives with rare earth ions on a 2D Kagome lattice. J Mater Chem C, 2016, 4: 541–550
Ge R, Li L, Su J, et al. Ultrafine defective RuO2 electrocatayst integrated on carbon cloth for robust water oxidation in acidic media. Adv Energy Mater, 2019, 9: 1901313
Li P, Wang M, Duan X, et al. Boosting oxygen evolution of single-atomic ruthenium through electronic coupling with cobalt-iron layered double hydroxides. Nat Commun, 2019, 10: 1711
Liu G, Li J, Fu J, et al. An oxygen-vacancy-rich semiconductor-supported bifunctional catalyst for efficient and stable zinc-air batteries. Adv Mater, 2018, 30: 1806761
Tong Y, Guo H, Liu D, et al. Vacancy engineering of iron-doped W18O49 nanoreactors for low-barrier electrochemical nitrogen reduction. Angew Chem Int Ed, 2020, 59: 7356–7361
Diaz-Morales O, Raaijman S, Kortlever R, et al. Iridium-based double perovskites for efficient water oxidation in acid media. Nat Commun, 2016, 7: 12363
Zhang L, Yuan H, Wang L, et al. The critical role of electrochemically activated adsorbates in neutral OER. Sci China Mater, 2020, 63: 2509–2516
Rossmeisl J, Logadottir A, Nørskov JK. Electrolysis of water on (oxidized) metal surfaces. Chem Phys, 2005, 319: 178–184
Norsko JK. Chemisorption on metal surfaces. Rep Prog Phys, 1999, 53: 1253–1295
Chen Z, Song Y, Cai J, et al. Tailoring the d-band centers enables Co4N nanosheets to be highly active for hydrogen evolution catalysis. Angew Chem Int Ed, 2018, 57: 5076–5080
Song Q, Li J, Wang S, et al. Enhanced electrocatalytic performance through body enrichment of Co-based bimetallic nanoparticles in situ embedded porous N-doped carbon spheres. Small, 2019, 15: 1903395
Acknowledgements
This work was supported by the National Key Research and Development Project (2018YFB1502401), the National Natural Science Foundation of China (21771018 and 21875004), the Royal Society and Newton Fund through Newton Advanced Fellowship award (NAFR1191294), the Program for Changjiang Scholars and Innovation Research Team in the University (IRT1205), the Fundamental Research Funds for the Central Universities, and the long-term subsidy mechanism from the Ministry of Finance and the Ministry of Education of China.
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Liu H, Wang Z, Kuang Y and Sun X conceived the research; Liu H, Wang Z and Wang S designed and carried out the experiments; Zhao X, Duan X, Liu H and Wang Z did the DFT calculations; Liu H, Wang Z and Li M draw the figures; all the authors analyzed the data; Liu H, Wang Z, Kuang Y and Sun X wrote the paper.
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Hai Liu is a PhD student at Beijing University of Chemical Technology (BUCT) under the supervision of Prof. Xiaoming Sun. His current research focuses on electrocatalytic water oxidation in acidic media.
Zhaolei Wang is a PhD student at BUCT under the supervision of Prof. Xiaoming Sun. His current research focuses on electrocatalytic water oxidation.
Yun Kuang obtained his BE and PhD degrees from BUCT in 2010 and 2015, respectively. He then joined the faculty of BUCT. He is now an associate professor in chemistry at the College of Chemistry, BUCT and a visiting associate professor in the Department of Chemistry, Stanford University. His current research interest mainly focuses on the synthesis, structure regulation and assembly of transitional metal-based nanostructures under control, as well as their application in catalysis and energy-related area.
Xiaoming Sun received his BSc degree and PhD degree from the Department of Chemistry, Tsinghua University in 2000 and 2005, respectively. After postdoctoral work at Stanford University, he joined the State Key Laboratory of Chemical Resource Engineering, BUCT in 2008. His main research interests focus on parathion and assembly of inorganic nanostructures, synthesis and separation of carbon nanomaterials and their composites, and structure control and opto-/eletro-property investigations of oxide nanoarrays.
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Rare-earth-regulated Ru-O interaction within the pyrochlore ruthenate for electrocatalytic oxygen evolution in acidic media
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Liu, H., Wang, Z., Li, M. et al. Rare-earth-regulated Ru-O interaction within the pyrochlore ruthenate for electrocatalytic oxygen evolution in acidic media. Sci. China Mater. 64, 1653–1661 (2021). https://doi.org/10.1007/s40843-020-1571-y
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DOI: https://doi.org/10.1007/s40843-020-1571-y