The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is a key performance-limiting step of rechargeable zinc-air batteries. Developing a reliable strategy to optimize the activity of Co occupied the tetrahedral site (Co) is crucial for enhancing electrocatalytic performance and still needs further elaborate elucidation. Here, Mo dopants were used as electron donors to construct low-valence Co sites in cobalt phosphide, resulting in downshifted -band centers and strengthened hybridization between Co 3 and P 3 orbitals. The negative charges are easier to accumulate on three antibonding orbitals of Co, promoting the desorption of oxygen intermediates, as evidenced using density functional theory calculations and spectroscopic investigations. The optimal catalyst delivers impressive ORR and OER performance, in terms of half-wave potential of 0.84 V for ORR and overpotential of 247 mV for OER. In general, this work opens a new opportunity to rationally regulate electronic structure of Co sites introducing an electron donor, as well as provides guidance for exploring electronic descriptors of tetrahedral sites.
氧还原反应（ORR）和氧进化反应（OER）是限制可充电锌-空气电池性能的关键步骤。开发一种可靠的策略来优化占据四面体位点（Co）的 Co 的活性，对于提高电催化性能至关重要，但仍需进一步详细阐明。在这里，掺杂钼作为电子供体在磷化钴中构建了低电价钴位点，从而导致带中心下移，并加强了钴 3 和 P 3 轨道之间的杂化。密度泛函理论计算和光谱研究证明，负电荷更容易聚集在 Co 的三个反键轨道上，从而促进氧中间产物的解吸。最佳催化剂具有令人印象深刻的 ORR 和 OER 性能，ORR 的半波电位为 0.84 V，OER 的过电位为 247 mV。总之，这项工作为合理调节引入电子供体的 Co 位点的电子结构提供了新的机遇，并为探索四面体位点的电子描述符提供了指导。
{"title":"Constructing electron-enriched Co tetrahedral sites to promote oxygen electrocatalysis in rechargeable zinc-air batteries","authors":"Jingrui Han, Jieshu Zhou, Wei Song, Hao Zhang, Ziyun Wang, Kangning Liu, Yong Li, Weijun Zhu, Xuhui Sun, Hongyan Liang","doi":"10.1016/j.apcatb.2024.124468","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124468","url":null,"abstract":"The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is a key performance-limiting step of rechargeable zinc-air batteries. Developing a reliable strategy to optimize the activity of Co occupied the tetrahedral site (Co) is crucial for enhancing electrocatalytic performance and still needs further elaborate elucidation. Here, Mo dopants were used as electron donors to construct low-valence Co sites in cobalt phosphide, resulting in downshifted -band centers and strengthened hybridization between Co 3 and P 3 orbitals. The negative charges are easier to accumulate on three antibonding orbitals of Co, promoting the desorption of oxygen intermediates, as evidenced using density functional theory calculations and spectroscopic investigations. The optimal catalyst delivers impressive ORR and OER performance, in terms of half-wave potential of 0.84 V for ORR and overpotential of 247 mV for OER. In general, this work opens a new opportunity to rationally regulate electronic structure of Co sites introducing an electron donor, as well as provides guidance for exploring electronic descriptors of tetrahedral sites.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"16 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141943014","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-02DOI: 10.1016/j.apcatb.2024.124463
Tian Tian, Peixin Zhu, Chun He, Ya Xiong, Jingyun Fang, Shuanghong Tian
As initial and important reactive species, surface O complexes are rarely investigated in catalytic ozonation, which might be one cause of dispute in mechanistic understanding. Herein, In-situ DRIFTS and premixing-standing experiments confirmed the generation of long-lived Mn-O* complexes upon O adsorption on surface Lewis acid sites of α-MnO. In α-MnO/O system, the oxidation rate of various pollutants showed a good linear correlation with their redox potentials, as well as the energy gap between the pollutants and Mn-O* complexes. Joint catalytic mechanism experiments and density functional theory calculations revealed that the oxidation of pollutants was boosted mainly because there was fast nonradical intermolecular electron transfer from the HOMO of pollutants to the LUMO of Mn-O* complexes. This study illustrates the significance of surface Mn-O* complex in catalytic ozonation and discloses an efficient nonradical catalytic ozonation process that is resistant to pH fluctuation and matrix interference.
作为最初的重要反应物，表面 O 复合物在催化臭氧过程中很少被研究，这可能是机理认识上存在争议的原因之一。在此，原位 DRIFTS 和预混立实验证实了 α-MnO 表面路易斯酸位点吸附 O 后生成长寿命 Mn-O* 复合物。在 α-MnO/O 体系中，各种污染物的氧化率与其氧化还原电位以及污染物与 Mn-O* 复合物之间的能隙呈良好的线性关系。联合催化机理实验和密度泛函理论计算表明，污染物的氧化率之所以得到提高，主要是因为污染物的 HOMO 与 Mn-O* 复合物的 LUMO 之间存在快速的非辐射分子间电子转移。这项研究说明了表面 Mn-O* 复合物在催化臭氧氧化过程中的重要作用，并揭示了一种高效的非辐射催化臭氧氧化过程，该过程不受 pH 值波动和基质干扰的影响。
{"title":"Surface Mn-O3* complex-mediated nonradical electron transfer for boosting catalytic ozonation of organic pollutants","authors":"Tian Tian, Peixin Zhu, Chun He, Ya Xiong, Jingyun Fang, Shuanghong Tian","doi":"10.1016/j.apcatb.2024.124463","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124463","url":null,"abstract":"As initial and important reactive species, surface O complexes are rarely investigated in catalytic ozonation, which might be one cause of dispute in mechanistic understanding. Herein, In-situ DRIFTS and premixing-standing experiments confirmed the generation of long-lived Mn-O* complexes upon O adsorption on surface Lewis acid sites of α-MnO. In α-MnO/O system, the oxidation rate of various pollutants showed a good linear correlation with their redox potentials, as well as the energy gap between the pollutants and Mn-O* complexes. Joint catalytic mechanism experiments and density functional theory calculations revealed that the oxidation of pollutants was boosted mainly because there was fast nonradical intermolecular electron transfer from the HOMO of pollutants to the LUMO of Mn-O* complexes. This study illustrates the significance of surface Mn-O* complex in catalytic ozonation and discloses an efficient nonradical catalytic ozonation process that is resistant to pH fluctuation and matrix interference.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"8 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141943024","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Electrochemical reduction of nitrate (NORR) to ammonia (NH/NH) offers promising prospects for NO treatment. However, this process still suffers from NH causing secondary pollution and catalyst deactivation in high-concentration NO wastewater. Herein, a high-performance system comprising a hematite (α-FeO) electrode and a water-resistant membrane achieved 97.6 % NO removal and 81.6 % NH as (NH)SO recovery at wastewater-level NO. The system exhibited an energy consumption of 62.2 kWh·Kg and a Faradaic efficiency of 85.9 %. spectroscopy and electrochemical measurements revealed that α-FeO acted as both an electron transfer mediator for reducing NO to NO and an active center for NH formation via NO/Fe(Ⅱ) redox. Density functional theory calculations identified *HNO to *NO as potential-determining step of NORR. Natural hematite-based system exhibited 74.8 % total inorganic nitrogen removal and 77.1 % NH recovery for actual photovoltaic wastewater. This study provides insights into the development of electrochemical systems for resourcefully treating NO-containing wastewater.
将硝酸盐（NORR）电化学还原为氨（NH/NH）为氮氧化物处理提供了广阔的前景。然而，在高浓度氮废水处理过程中，该工艺仍存在 NH 造成二次污染和催化剂失活的问题。在本文中，一个由赤铁矿（α-FeO）电极和防水膜组成的高性能系统实现了 97.6% 的 NO 去除率和 81.6% 的 NH（NH）SO 回收率。该系统的能耗为 62.2 kWh-Kg，法拉第效率为 85.9%。光谱和电化学测量显示，α-FeO 既是将 NO 还原成 NO 的电子转移介质，也是通过 NO/Fe(Ⅱ)氧化还原形成 NH 的活性中心。密度泛函理论计算确定 *HNO 到 *NO 是 NORR 的电位决定步骤。天然赤铁矿系统对实际光伏废水的无机氮总去除率为 74.8%，NH 回收率为 77.1%。这项研究为开发资源化处理含氮废水的电化学系统提供了启示。
{"title":"In-situ electrochemical upcycling ammonia from wastewater-level nitrate with a natural hematite electrode: Regulation, performance, and application","authors":"Xing Wu, Zhenhui Song, Zhigong Liu, Xi Tang, Fubing Yao, Feiping Zhao, Xiaobo Min, Chong-Jian Tang","doi":"10.1016/j.apcatb.2024.124467","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124467","url":null,"abstract":"Electrochemical reduction of nitrate (NORR) to ammonia (NH/NH) offers promising prospects for NO treatment. However, this process still suffers from NH causing secondary pollution and catalyst deactivation in high-concentration NO wastewater. Herein, a high-performance system comprising a hematite (α-FeO) electrode and a water-resistant membrane achieved 97.6 % NO removal and 81.6 % NH as (NH)SO recovery at wastewater-level NO. The system exhibited an energy consumption of 62.2 kWh·Kg and a Faradaic efficiency of 85.9 %. spectroscopy and electrochemical measurements revealed that α-FeO acted as both an electron transfer mediator for reducing NO to NO and an active center for NH formation via NO/Fe(Ⅱ) redox. Density functional theory calculations identified *HNO to *NO as potential-determining step of NORR. Natural hematite-based system exhibited 74.8 % total inorganic nitrogen removal and 77.1 % NH recovery for actual photovoltaic wastewater. This study provides insights into the development of electrochemical systems for resourcefully treating NO-containing wastewater.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"25 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141943029","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-02DOI: 10.1016/j.apcatb.2024.124465
Yue Shi, Jiawei Fei, Hongdong Li, Caixia Li, Tianrong Zhan, Jianping Lai, Lei Wang
Amorphous metallene is a prospective catalyst due to disordered atomic arrangement and abundant defects/edges. However, challenges persist in preparing amorphous metallene with atomic interface, primarily due to thermodynamic impediment of unconventional phase and difficulty in precise controlling of atomic interface. Here, we synthesized a new class of amorphous RuGa metallene (A-RuGa metallene) with abundant atomic interface by introducing trace atomic-dispersed Ga. The atomic interface between Ga-coordinated Ru and Ru achieves monometallic synergism during alkaline hydrogen evolution reaction. The turnover frequency value of A-RuGa metallene reaches 67 s at −0.1 V RHE. Meanwhile, the mass activity of A-RuGa metallene in anion exchange membrane electrolyzer reaches 5.2 A mg at 2.0 V, firstly surpassing commercial Pt/C (1.0 A mg). The trace atomic dispersed Ga could change the local valence state of monometallic Ru, thus promoting water adsorption and dissociation, optimizing H* adsorption and accelerating H* transport at the atomic level.
由于无序的原子排列和丰富的缺陷/边缘，非晶态茂金属是一种前景广阔的催化剂。然而，制备具有原子界面的非晶态茂金属仍然面临挑战，这主要是由于非常规相的热力学障碍和原子界面的精确控制困难。在这里，我们通过引入痕量原子分散镓，合成了一类具有丰富原子界面的新型非晶钌镓金属（A-RuGa metallene）。在碱性氢进化反应中，Ga 配位的 Ru 与 Ru 之间的原子界面实现了单金属协同作用。在 -0.1 V RHE 条件下，A-RuGa 茂金属的翻转频率值达到 67 s。同时，A-RuGa 茂金属在阴离子交换膜电解槽中的质量活度在 2.0 V 时达到 5.2 A mg，首次超过了商用 Pt/C（1.0 A mg）。微量原子分散的 Ga 可以改变单金属 Ru 的局部价态，从而促进水的吸附和解离，优化 H* 的吸附，并在原子水平上加速 H* 的传输。
{"title":"Amorphous Ru-based metallene with monometallic atomic interfaces for electrocatalytic hydrogen evolution in anion exchange membrane electrolyzer","authors":"Yue Shi, Jiawei Fei, Hongdong Li, Caixia Li, Tianrong Zhan, Jianping Lai, Lei Wang","doi":"10.1016/j.apcatb.2024.124465","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124465","url":null,"abstract":"Amorphous metallene is a prospective catalyst due to disordered atomic arrangement and abundant defects/edges. However, challenges persist in preparing amorphous metallene with atomic interface, primarily due to thermodynamic impediment of unconventional phase and difficulty in precise controlling of atomic interface. Here, we synthesized a new class of amorphous RuGa metallene (A-RuGa metallene) with abundant atomic interface by introducing trace atomic-dispersed Ga. The atomic interface between Ga-coordinated Ru and Ru achieves monometallic synergism during alkaline hydrogen evolution reaction. The turnover frequency value of A-RuGa metallene reaches 67 s at −0.1 V RHE. Meanwhile, the mass activity of A-RuGa metallene in anion exchange membrane electrolyzer reaches 5.2 A mg at 2.0 V, firstly surpassing commercial Pt/C (1.0 A mg). The trace atomic dispersed Ga could change the local valence state of monometallic Ru, thus promoting water adsorption and dissociation, optimizing H* adsorption and accelerating H* transport at the atomic level.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"112 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141943015","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-08-02DOI: 10.1016/j.apcatb.2024.124464
Ziting Wang, Mihang Yao, Xiaoyu Niu, Yujun Zhu
Resistance to alkali metal poisoning remains a challenge for Ce-based denitration (de-NO) catalysts. In this paper, improved low-temperature performance and resistance to K poisoning were achieved by phosphorylating CeSnO. The activity tests revealed that the phosphorylated CeSnO (3 wt%P/CeSn) exhibited over 90 % NO conversion at 190–450 °C and >90 % NO conversion at 240–400 °C even after K poisoning. The mechanism of phosphorylation treatment against K poisoning was investigated by many characterizations and DFT calculation. The results showed that the phosphorylation treatment facilitated the interaction between Ce and Sn, and K interacts more preferentially with PO species. This prevents K from destroying the Ce-O-Sn structure to form a Ce-O-K structure, which in turn maintained the catalyst’s redox properties. Moreover, the phosphorylation treatment supplemented the acidity of 3 wt%P/CeSn compared with CeSnO. This effectively mitigated the reduction of acidity caused by K and ensured the adsorption and activation of NH on the catalyst surface.
抗碱金属中毒仍然是铈基脱硝（脱氮）催化剂面临的一项挑战。本文通过对 CeSnO 进行磷酸化处理，提高了其低温性能和抗 K 中毒能力。活性测试表明，即使在 K 中毒后，磷酸化 CeSnO（3 wt%P/CeSn）在 190-450 ℃ 时的 NO 转化率超过 90%，在 240-400 ℃ 时的 NO 转化率大于 90%。通过多种表征和 DFT 计算研究了磷酸化处理 K 中毒的机理。结果表明，磷化处理促进了 Ce 和 Sn 之间的相互作用，而 K 更倾向于与 PO 物种相互作用。这防止了 K 破坏 Ce-O-Sn 结构，形成 Ce-O-K 结构，从而保持了催化剂的氧化还原特性。此外，与 CeSnO 相比，磷化处理补充了 3 wt%P/CeSn 的酸性。这有效缓解了 K 导致的酸度降低，确保了催化剂表面对 NH 的吸附和活化。
{"title":"Excellent low-temperature activity and resistance to K-poisoning in NH3-SCR de-NOx reaction over CeSnOx with phosphorylation treatment catalyst","authors":"Ziting Wang, Mihang Yao, Xiaoyu Niu, Yujun Zhu","doi":"10.1016/j.apcatb.2024.124464","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124464","url":null,"abstract":"Resistance to alkali metal poisoning remains a challenge for Ce-based denitration (de-NO) catalysts. In this paper, improved low-temperature performance and resistance to K poisoning were achieved by phosphorylating CeSnO. The activity tests revealed that the phosphorylated CeSnO (3 wt%P/CeSn) exhibited over 90 % NO conversion at 190–450 °C and >90 % NO conversion at 240–400 °C even after K poisoning. The mechanism of phosphorylation treatment against K poisoning was investigated by many characterizations and DFT calculation. The results showed that the phosphorylation treatment facilitated the interaction between Ce and Sn, and K interacts more preferentially with PO species. This prevents K from destroying the Ce-O-Sn structure to form a Ce-O-K structure, which in turn maintained the catalyst’s redox properties. Moreover, the phosphorylation treatment supplemented the acidity of 3 wt%P/CeSn compared with CeSnO. This effectively mitigated the reduction of acidity caused by K and ensured the adsorption and activation of NH on the catalyst surface.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"7 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141943016","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The non-covalent interaction that appears along with electronic tuning is often overlooked in interpreting the oxygen reduction reaction (ORR) dynamics, resulting in a limited understanding of the governing principles. Herein, through intricately engineering pedant substituents on porphyrins backbones, Co-N moieties featuring varied electronic configurations served as an exemplary model to elucidate the role of hydrogen bonding interaction appears along with electronic tuning in determining 2e ORR performance. Co-TEPP with an electron-deficient Co-N moiety emerges as a standout performer for O-to-HO conversion. Upon covalently linking the Co-TEPP monomer on rGO to form robust organic polymer structures (Co-TEPP-COP/rGO), superior HO selectivity (> 95 %), remarkable HO production rate (∼18.8 mol g h), and excellent performance durability are identified. Such optimized HO electrosynthesis could be attributed to the suppressed hydrogen bonding interaction between *OOH and electron-deficient Co-N moiety, which consequently weakens *OOH binding strength to favor HO electrosynthesis.
在解释氧还原反应（ORR）动力学时，随着电子调谐而出现的非共价相互作用往往被忽视，导致对其原理的理解有限。在这里，通过对卟啉骨架上的取代基进行复杂的工程设计，以具有不同电子构型的 Co-N 分子为典范，阐明了氢键相互作用和电子调谐在决定 2e ORR 性能中的作用。具有缺电子 Co-N 分子的 Co-TEPP 在 O 到HO 的转化中表现突出。在将 Co-TEPP 单体共价连接到 rGO 上以形成坚固的有机聚合物结构（Co-TEPP-COP/rGO）后，发现了卓越的 HO 选择性（> 95%）、显著的 HO 产率（∼18.8 mol g h）和出色的性能持久性。这种优化的 HO 电合成可能是由于 *OOH 与缺电子 Co-N 分子之间的氢键相互作用受到抑制，从而削弱了 *OOH 的结合强度，有利于 HO 的电合成。
{"title":"Suppressing the hydrogen bonding interaction with *OOH toward efficient H2O2 electrosynthesis via remote electronic tuning of Co-N4","authors":"Jiawei Zhang, Hongwei Zeng, Bingling He, Ying Liu, Jing Xu, Tengfei Niu, Chengsi Pan, Ying Zhang, Yang Lou, Yao Wang, Yuming Dong, Yongfa Zhu","doi":"10.1016/j.apcatb.2024.124448","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124448","url":null,"abstract":"The non-covalent interaction that appears along with electronic tuning is often overlooked in interpreting the oxygen reduction reaction (ORR) dynamics, resulting in a limited understanding of the governing principles. Herein, through intricately engineering pedant substituents on porphyrins backbones, Co-N moieties featuring varied electronic configurations served as an exemplary model to elucidate the role of hydrogen bonding interaction appears along with electronic tuning in determining 2e ORR performance. Co-TEPP with an electron-deficient Co-N moiety emerges as a standout performer for O-to-HO conversion. Upon covalently linking the Co-TEPP monomer on rGO to form robust organic polymer structures (Co-TEPP-COP/rGO), superior HO selectivity (> 95 %), remarkable HO production rate (∼18.8 mol g h), and excellent performance durability are identified. Such optimized HO electrosynthesis could be attributed to the suppressed hydrogen bonding interaction between *OOH and electron-deficient Co-N moiety, which consequently weakens *OOH binding strength to favor HO electrosynthesis.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"25 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141943020","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-31DOI: 10.1016/j.apcatb.2024.124462
Chenlu Yang, Wenhui Ling, Yanping Zhu, Yunxiao Yang, Shu Dong, Chengyu Wu, Zhangrui Wang, Shuai Yang, Jun Li, Guoliang Wang, Yifan Huang, Bo Yang, Qingqing Cheng, Zhi Liu, Hui Yang
Dynamic evolutionary hypervalent Ir species (HVI) plays a decisive role in promoting the catalytic activity towards acidic oxygen evolution reaction (OER) on Ir-based electrocatalysts, but regulating the efficient formation of HVI remains a big challenge. Herein we propose surface hydroxylation engineering to accelerate the formation of HVI along the OER process on the OH-rich IrO/TiO electrocatalyst. In-situ/operando spectroscopies demonstrate that the high concentration OH ligand accelerates the formation of HVI. DFT calculation clarifies that the dynamically evolved HVI benefits to weakening the adsorption free energy and thus boosting the OER kinetics. Differential electrochemical mass spectrometry with O isotope labelling experiment further unveils that the OH ligand directly participates in the OER cycle, facilitating the rapid oxidation of Ir to Ir and the O-O bond formation. PEM water electrolyzer with the optimized IrO/TiO electrocatalyst delivers a low cell voltage of 1.787 V at 2 Acm with an inaccessible low Ir usage of ca. 0.08 g/kW, while maintaining a good stability over 350 h, with an estimated cost of US$0.88 kg of H, much lower than 2026 US-DOE target.
动态演化的超价 Ir 物种（HVI）在促进 Ir 基电催化剂对酸性氧进化反应（OER）的催化活性方面起着决定性作用，但调节 HVI 的有效形成仍然是一个巨大的挑战。在此，我们提出了表面羟基化工程，以加速富含羟基的 IrO/TiO 电催化剂上 OER 过程中 HVI 的形成。原位/操作光谱证明，高浓度 OH 配体加速了 HVI 的形成。DFT 计算表明，动态演化的 HVI 有利于削弱吸附自由能，从而促进 OER 动力学。差分电化学质谱与 O 同位素标记实验进一步揭示，OH 配体直接参与了 OER 循环，促进了 Ir 快速氧化为 Ir 和 O-O 键的形成。使用优化的 IrO/TiO 电催化剂的 PEM 水电解槽在 2 Acm 时的电池电压低至 1.787 V，Ir 用量低至约 0.08 g/kW，同时在 350 小时内保持良好的稳定性，估计成本为 0.88 美元/千克 H，远低于 2026 年美国能源部的目标。
{"title":"Surface hydroxylation engineering to boost oxygen evolution reaction on IrO2/TiO2 for PEM water electrolyzer","authors":"Chenlu Yang, Wenhui Ling, Yanping Zhu, Yunxiao Yang, Shu Dong, Chengyu Wu, Zhangrui Wang, Shuai Yang, Jun Li, Guoliang Wang, Yifan Huang, Bo Yang, Qingqing Cheng, Zhi Liu, Hui Yang","doi":"10.1016/j.apcatb.2024.124462","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124462","url":null,"abstract":"Dynamic evolutionary hypervalent Ir species (HVI) plays a decisive role in promoting the catalytic activity towards acidic oxygen evolution reaction (OER) on Ir-based electrocatalysts, but regulating the efficient formation of HVI remains a big challenge. Herein we propose surface hydroxylation engineering to accelerate the formation of HVI along the OER process on the OH-rich IrO/TiO electrocatalyst. In-situ/operando spectroscopies demonstrate that the high concentration OH ligand accelerates the formation of HVI. DFT calculation clarifies that the dynamically evolved HVI benefits to weakening the adsorption free energy and thus boosting the OER kinetics. Differential electrochemical mass spectrometry with O isotope labelling experiment further unveils that the OH ligand directly participates in the OER cycle, facilitating the rapid oxidation of Ir to Ir and the O-O bond formation. PEM water electrolyzer with the optimized IrO/TiO electrocatalyst delivers a low cell voltage of 1.787 V at 2 Acm with an inaccessible low Ir usage of ca. 0.08 g/kW, while maintaining a good stability over 350 h, with an estimated cost of US$0.88 kg of H, much lower than 2026 US-DOE target.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"39 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141943017","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-31DOI: 10.1016/j.apcatb.2024.124461
Jianqing Zhou, Pengfei Li, Xinyi Xia, Yi Zhao, Zhihao Hu, Yunlong Xie, Lun Yang, Yisi Liu, Yue Du, Qiancheng Zhou, Luo Yu, Ying Yu
d‐band center engineering is an effective approach to manipulate the electronic structure of an electrocatalyst for boosting water splitting performance. However, it is still challenging to precisely tailor the electronic structure with an optimized d‐band center for efficient hydrogen and oxygen evolution reactions (HER and OER) on one single catalyst simultaneously. Focusing on nickel sulfide (NiS), herein we applied dual-atom modification to precisely regulate the d‐band center of NiS, which dramatically enhances its bifunctional activity with outstanding HER and OER performance. Specifically, the V and Fe co-modified NiS achieves ultra-low overpotentials of 68 and 190 mV to output 10 mA cm in 1 M KOH for HER and OER, respectively. Theoretical calculations reveal that the strong electronic interactions between Ni 3d and V 3d/Fe 3d orbitals effectively tailor the d‐band center of NiS, resulting in optimized HER and OER intermediate adsorption, thus boosting the HER and OER simultaneously.
d 带中心工程是操纵电催化剂电子结构以提高水分离性能的一种有效方法。然而，在单一催化剂上同时精确定制具有优化 d 波段中心的电子结构，以实现高效的氢和氧进化反应（HER 和 OER），仍然具有挑战性。在此，我们以硫化镍（NiS）为研究对象，采用双原子修饰技术精确调节 NiS 的 d 带中心，从而显著提高了其双功能活性，使其具有出色的 HER 和 OER 性能。具体而言，V 和 Fe 共修饰的 NiS 在 1 M KOH 中分别实现了 68 和 190 mV 的超低过电位，输出 10 mA cm 的 HER 和 OER。理论计算显示，Ni 3d 和 V 3d/Fe 3d 轨道之间的强电子相互作用有效地调整了 NiS 的 d 带中心，优化了 HER 和 OER 中间吸附，从而同时提高了 HER 和 OER。
{"title":"Precisely tailoring the d-band center of nickel sulfide for boosting overall water splitting","authors":"Jianqing Zhou, Pengfei Li, Xinyi Xia, Yi Zhao, Zhihao Hu, Yunlong Xie, Lun Yang, Yisi Liu, Yue Du, Qiancheng Zhou, Luo Yu, Ying Yu","doi":"10.1016/j.apcatb.2024.124461","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124461","url":null,"abstract":"d‐band center engineering is an effective approach to manipulate the electronic structure of an electrocatalyst for boosting water splitting performance. However, it is still challenging to precisely tailor the electronic structure with an optimized d‐band center for efficient hydrogen and oxygen evolution reactions (HER and OER) on one single catalyst simultaneously. Focusing on nickel sulfide (NiS), herein we applied dual-atom modification to precisely regulate the d‐band center of NiS, which dramatically enhances its bifunctional activity with outstanding HER and OER performance. Specifically, the V and Fe co-modified NiS achieves ultra-low overpotentials of 68 and 190 mV to output 10 mA cm in 1 M KOH for HER and OER, respectively. Theoretical calculations reveal that the strong electronic interactions between Ni 3d and V 3d/Fe 3d orbitals effectively tailor the d‐band center of NiS, resulting in optimized HER and OER intermediate adsorption, thus boosting the HER and OER simultaneously.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"71 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141943023","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-30DOI: 10.1016/j.apcatb.2024.124456
Amol R. Jadhav, Xinghui Liu, P. Silambarasan, Vinit Kanade, Yang Liu, Ta Thi Thuy Nga, Taehun Yang, My Tran Kim, Yeonsu Han, Taesung Kim, Xiaodong Shao, Chunyi Zhi, Chung-Li Dong, Hyoyoung Lee
Developing highly efficient and selective electrocatalysts for the chlorine evolution reaction (CER) in the chloralkali industry is of great importance. Here, we report the discovery of a new electrocatalyst for CER consisting of atomically dispersed Ru sites on surface tensile strained TiO (Ru-S-TiO). The single-atom Ru species were stabilized on the strained TiO surface by strong metal-support interactions. The Ru-S-TiO is highly efficient, initiating CER at only 5 mV above the E, and has shown excellent stability for over 100 hours. It exhibited >95 % CER selectivity even in acidic media with low Cl concentrations (0.2 M). Our results demonstrate that the strong metal-support interactions between the atomically dispersed Ru species and the strained TiO surface are crucial for the high catalytic activity, selectivity, and stability of Ru-S-TiO for CER. Ru-S-TiO holds great promise as a viable alternative to existing mixed metal oxides-based electrocatalysts for CER in the chloralkali industry.
{"title":"Stable and efficient chlorine evolution reaction with atomically dispersed Ru on surface tensile strained TiO2","authors":"Amol R. Jadhav, Xinghui Liu, P. Silambarasan, Vinit Kanade, Yang Liu, Ta Thi Thuy Nga, Taehun Yang, My Tran Kim, Yeonsu Han, Taesung Kim, Xiaodong Shao, Chunyi Zhi, Chung-Li Dong, Hyoyoung Lee","doi":"10.1016/j.apcatb.2024.124456","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124456","url":null,"abstract":"Developing highly efficient and selective electrocatalysts for the chlorine evolution reaction (CER) in the chloralkali industry is of great importance. Here, we report the discovery of a new electrocatalyst for CER consisting of atomically dispersed Ru sites on surface tensile strained TiO (Ru-S-TiO). The single-atom Ru species were stabilized on the strained TiO surface by strong metal-support interactions. The Ru-S-TiO is highly efficient, initiating CER at only 5 mV above the E, and has shown excellent stability for over 100 hours. It exhibited >95 % CER selectivity even in acidic media with low Cl concentrations (0.2 M). Our results demonstrate that the strong metal-support interactions between the atomically dispersed Ru species and the strained TiO surface are crucial for the high catalytic activity, selectivity, and stability of Ru-S-TiO for CER. Ru-S-TiO holds great promise as a viable alternative to existing mixed metal oxides-based electrocatalysts for CER in the chloralkali industry.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"26 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141943018","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-07-29DOI: 10.1016/j.apcatb.2024.124459
Guotai Sun, Zige Tai, Jianjun Zhang, Bei Cheng, Huogen Yu, Jiaguo Yu
Photocatalytic H evolution coupled with organic oxidation could replace the slow four-electron water oxidation and utilize charge carriers to obtain high-valued chemicals. Herein, inorganic CdZnS quantum dots (QDs) are skillfully deposited on g-CN nanospheres to construct an inorganic-polymeric S-scheme heterostructure. The CN-CdZnS photocatalyst presents enhanced light absorption, abundant active sites, and intimate interface contact. The optimized composite exhibits an enhanced H evolution rate of 582.3 μmol/g/h and a furfuryl alcohol (FAL) conversion of 84.2 %. Femtosecond transient absorption (fs-TA) spectroscopy, irradiation X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), and theoretical calculation (DFT) verify the S-scheme mechanism, which promotes charge separation and strengthens carrier redox ability. infrared spectra reveal that FAL is first activated to CHO radical by holes in CdZnS and further oxidized to furfural (FF) with dehydrogenation of its hydroxyl group. This work supplies new insight into designing efficient photocatalysts for H generation and organic synthesis.
光催化氢进化与有机物氧化相结合，可以取代缓慢的四电子水氧化，并利用电荷载流子获得高价值的化学物质。在这里，无机 CdZnS 量子点（QDs）被巧妙地沉积在 g-CN 纳米球上，从而构建了一种无机聚合物 S 型异质结构。CN-CdZnS 光催化剂具有更强的光吸收能力、丰富的活性位点和亲密的界面接触。优化后的复合材料表现出更高的 H 演化率（582.3 μmol/g/h）和 84.2% 的糠醇（FAL）转化率。飞秒瞬态吸收 (fs-TA) 光谱、辐照 X 射线光电子能谱 (XPS)、电子顺磁共振 (EPR) 和理论计算 (DFT) 验证了促进电荷分离和增强载体氧化还原能力的 S 型机制。这项研究为设计高效的光催化剂用于氢气生成和有机合成提供了新的视角。
{"title":"Bifunctional g-C3N4 nanospheres/CdZnS QDs S-scheme photocatalyst with boosted H2 evolution and furfural synthesis mechanism","authors":"Guotai Sun, Zige Tai, Jianjun Zhang, Bei Cheng, Huogen Yu, Jiaguo Yu","doi":"10.1016/j.apcatb.2024.124459","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124459","url":null,"abstract":"Photocatalytic H evolution coupled with organic oxidation could replace the slow four-electron water oxidation and utilize charge carriers to obtain high-valued chemicals. Herein, inorganic CdZnS quantum dots (QDs) are skillfully deposited on g-CN nanospheres to construct an inorganic-polymeric S-scheme heterostructure. The CN-CdZnS photocatalyst presents enhanced light absorption, abundant active sites, and intimate interface contact. The optimized composite exhibits an enhanced H evolution rate of 582.3 μmol/g/h and a furfuryl alcohol (FAL) conversion of 84.2 %. Femtosecond transient absorption (fs-TA) spectroscopy, irradiation X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), and theoretical calculation (DFT) verify the S-scheme mechanism, which promotes charge separation and strengthens carrier redox ability. infrared spectra reveal that FAL is first activated to CHO radical by holes in CdZnS and further oxidized to furfural (FF) with dehydrogenation of its hydroxyl group. This work supplies new insight into designing efficient photocatalysts for H generation and organic synthesis.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"17 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141943022","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：