Janak, Vijay S. Sapner, Bhaskar R. Sathe and Sadhika Khullar
{"title":"Construction of efficient Pb(ii) carboxylate catalysts for the oxygen and hydrogen evolution reactions†","authors":"Janak, Vijay S. Sapner, Bhaskar R. Sathe and Sadhika Khullar","doi":"10.1039/D4DT02958E","DOIUrl":null,"url":null,"abstract":"<p >The development of cost-effective and efficient electrocatalysts can solve the problems associated with the production of energy <em>via</em> water-splitting reactions. In this work, we have focused on two lead-based coordination polymers (CPs), namely, {[Pb<small><sub>2</sub></small>(TPBN)(HBTC)<small><sub>2</sub></small>]<small><sub>2</sub></small>·2.5H<small><sub>2</sub></small>O}<small><sub><em>n</em></sub></small> (<strong>CP1</strong>) and {[Pb<small><sub>2</sub></small>(TPBN)(NDC)<small><sub>2</sub></small>]·H<small><sub>2</sub></small>O}<small><sub><em>n</em></sub></small> (<strong>CP2</strong>), that were synthesized by self-assembly method at room temperature in good yields. The two-dimensional structures of <strong>CP1</strong> and <strong>CP2</strong> were determined by single-crystal X-ray diffraction studies. Their phase purity and thermal stability were confirmed by powder X-ray diffraction and TGA analysis, respectively. In addition to this, Hirshfeld surface analysis of <strong>CP1</strong> and <strong>CP2</strong> revealed the key differences in their intermolecular interactions. Both <strong>CP1</strong> and <strong>CP2</strong> were employed for HER and OER. It has been found that the change in the carboxylate from BTC to NDC resulted in better electrocatalytic activity towards water-splitting reactions. This may be attributed to the presence of more π character in NDC compared to BTC, which makes the electron flow much easier for HER process. <strong>CP1</strong> and <strong>CP2</strong> showed overpotential values of −0.58 V and −0.55 V, respectively, in 1 M H<small><sub>2</sub></small>SO<small><sub>4</sub></small> to reach a 10 mA cm<small><sup>−2</sup></small> current density with Tafel slopes of 31 mV dec<small><sup>−1</sup></small> and 25 mV dec<small><sup>−1</sup></small>, respectively. For the OER process, <strong>CP1</strong> and <strong>CP2</strong> exhibited overpotentials of 590 mV and 470 mV, respectively, in 1 M KOH at a current density of 50 mA cm<small><sup>−2</sup></small> with Tafel slope values of 81 mV dec<small><sup>−1</sup></small> and 56 mV dec<small><sup>−1</sup></small>, respectively. Turnover frequency (TOF) values of <strong>CP1</strong> and <strong>CP2</strong> were 1.05 s<small><sup>−1</sup></small> and 3.21 s<small><sup>−1</sup></small> for OER and 1.97 s<small><sup>−1</sup></small> and 9.65 s<small><sup>−1</sup></small> for HER, respectively. These results indicate that both CPs can act as highly efficient electrocatalysts for clean energy production.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 3","pages":" 1087-1102"},"PeriodicalIF":3.5000,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/dt/d4dt02958e","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
The development of cost-effective and efficient electrocatalysts can solve the problems associated with the production of energy via water-splitting reactions. In this work, we have focused on two lead-based coordination polymers (CPs), namely, {[Pb2(TPBN)(HBTC)2]2·2.5H2O}n (CP1) and {[Pb2(TPBN)(NDC)2]·H2O}n (CP2), that were synthesized by self-assembly method at room temperature in good yields. The two-dimensional structures of CP1 and CP2 were determined by single-crystal X-ray diffraction studies. Their phase purity and thermal stability were confirmed by powder X-ray diffraction and TGA analysis, respectively. In addition to this, Hirshfeld surface analysis of CP1 and CP2 revealed the key differences in their intermolecular interactions. Both CP1 and CP2 were employed for HER and OER. It has been found that the change in the carboxylate from BTC to NDC resulted in better electrocatalytic activity towards water-splitting reactions. This may be attributed to the presence of more π character in NDC compared to BTC, which makes the electron flow much easier for HER process. CP1 and CP2 showed overpotential values of −0.58 V and −0.55 V, respectively, in 1 M H2SO4 to reach a 10 mA cm−2 current density with Tafel slopes of 31 mV dec−1 and 25 mV dec−1, respectively. For the OER process, CP1 and CP2 exhibited overpotentials of 590 mV and 470 mV, respectively, in 1 M KOH at a current density of 50 mA cm−2 with Tafel slope values of 81 mV dec−1 and 56 mV dec−1, respectively. Turnover frequency (TOF) values of CP1 and CP2 were 1.05 s−1 and 3.21 s−1 for OER and 1.97 s−1 and 9.65 s−1 for HER, respectively. These results indicate that both CPs can act as highly efficient electrocatalysts for clean energy production.
期刊介绍:
Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.