The electrochemical nitric oxide reduction reaction (eNORR) is meticulously investigated as an alternative to the energy intensive Haber-Bosch process to produce Ammonia (NH). However, the eNORR is hindered by NH selectivity due to side reactions and mass-transfer limitations. In this work, we rationally designed copper nanowires (Cu NWs) infused in the lotus-root-like multi-nano-channels of the porous N-doped carbon nanorods (Cu-mNCNR) for a high selective eNORR to synthesize NH at ambient conditions. The optimized catalyst, Cu-mNCNR2, has achieved the highest NH Faradaic efficiency of 79% with NH yield rate of 34.5 μmol cm h at −0.4 V. Moreover, the Cu-mNCNR2 has demonstrated a vigorous performance in the 24 h continuous NO electrolysis to produce NH. Additionally, a prototype device, the Zn-NO battery, was demonstrated. This study shows that the rational design of a catalyst considering mass-transfer limitations is crucial to achieving high selective NH electrosynthesis in eNORR.
电化学一氧化氮还原反应（eNORR）作为生产氨气（NH）的高能耗哈伯-博什工艺的替代方法，受到了细致的研究。然而，由于副反应和传质的限制，eNORR 受阻于 NH 的选择性。在这项工作中，我们合理地设计了铜纳米线（Cu NWs），将其注入多孔掺杂 N 的碳纳米棒（Cu-mNCNR）的莲藕状多纳米通道中，从而在环境条件下合成高选择性 eNORR。优化后的催化剂 Cu-mNCNR2 在 -0.4 V 条件下的 NH 法拉第效率最高，达到 79%，NH 产率为 34.5 μmol cm h。此外，Cu-mNCNR2 在连续 24 小时电解 NO 生成 NH 的过程中表现出了强劲的性能。此外，还展示了 Zn-NO 电池的原型装置。这项研究表明，要在 eNORR 中实现高选择性 NH 电合成，合理设计催化剂并考虑质量转移限制至关重要。
{"title":"Selective electrosynthesis of ammonia via nitric oxide electroreduction catalyzed by copper nanowires infused in nitrogen-doped carbon nanorods","authors":"Dinesh Dhanabal, Yuyeon Song, Seoyoung Jang, Sangaraju Shanmugam","doi":"10.1016/j.apcatb.2024.124577","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124577","url":null,"abstract":"The electrochemical nitric oxide reduction reaction (eNORR) is meticulously investigated as an alternative to the energy intensive Haber-Bosch process to produce Ammonia (NH). However, the eNORR is hindered by NH selectivity due to side reactions and mass-transfer limitations. In this work, we rationally designed copper nanowires (Cu NWs) infused in the lotus-root-like multi-nano-channels of the porous N-doped carbon nanorods (Cu-mNCNR) for a high selective eNORR to synthesize NH at ambient conditions. The optimized catalyst, Cu-mNCNR2, has achieved the highest NH Faradaic efficiency of 79% with NH yield rate of 34.5 μmol cm h at −0.4 V. Moreover, the Cu-mNCNR2 has demonstrated a vigorous performance in the 24 h continuous NO electrolysis to produce NH. Additionally, a prototype device, the Zn-NO battery, was demonstrated. This study shows that the rational design of a catalyst considering mass-transfer limitations is crucial to achieving high selective NH electrosynthesis in eNORR.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142250000","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}
A series of Pd/yCoAlO (where y represents the Co/AlO mass ratio, ranging from 0 to 20.0 wt%) catalysts for CH combustion were synthesized, among which the Pd/15CoAlO catalyst exhibited excellent activity, stability and water resistance. HRTEM, XRD, and Raman results indicated that the Pd/15CoAlO catalyst comprised two phases, namely CoAlO and CoO. H-TPR, O-TPD, and in-situ DRIFTS revealed that Pd/15CoAlO featuring Pd-Co composite interfaces strengthened the anchoring of PdO and facilitated electron transfer between Pd-Co interfaces. Moreover, active oxygen species were enriched at the interface, which promoted the reaction pathway involving the change from methoxy to formate, rather than from methyl to formate. Multiple characterizations and analyses indicated that Pd/15CoAlO exhibited a MSI weaker than the Pd-CoO interface but stronger than that observed at the Pd-AlO interface. The appropriate level of interaction avoided the excessive oxidation of Pd, ensuring the presence of a substantial quantity of unsaturated Pd sites.
{"title":"A highly active and stable Pd/15CoAlOx catalyst with Pd-Co composite interfaces for methane combustion","authors":"Jieying Cai, Shenghai Wu, Miaomiao Liu, Yan Zhang, Meng Wang, Yun Liu, Yunbo Yu, Wenpo Shan","doi":"10.1016/j.apcatb.2024.124559","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124559","url":null,"abstract":"A series of Pd/yCoAlO (where y represents the Co/AlO mass ratio, ranging from 0 to 20.0 wt%) catalysts for CH combustion were synthesized, among which the Pd/15CoAlO catalyst exhibited excellent activity, stability and water resistance. HRTEM, XRD, and Raman results indicated that the Pd/15CoAlO catalyst comprised two phases, namely CoAlO and CoO. H-TPR, O-TPD, and in-situ DRIFTS revealed that Pd/15CoAlO featuring Pd-Co composite interfaces strengthened the anchoring of PdO and facilitated electron transfer between Pd-Co interfaces. Moreover, active oxygen species were enriched at the interface, which promoted the reaction pathway involving the change from methoxy to formate, rather than from methyl to formate. Multiple characterizations and analyses indicated that Pd/15CoAlO exhibited a MSI weaker than the Pd-CoO interface but stronger than that observed at the Pd-AlO interface. The appropriate level of interaction avoided the excessive oxidation of Pd, ensuring the presence of a substantial quantity of unsaturated Pd sites.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205116","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 : 2024-09-05DOI: 10.1016/j.apcatb.2024.124561
Muhammad Ajmal, Shishi Zhang, Xiaolei Guo, Xiaokang Liu, Chengxiang Shi, Ruijie Gao, Zhen-Feng Huang, Lun Pan, Xiangwen Zhang, Ji-Jun Zou
Metal oxyhydroxide (MOOH) through irreversible reconstructed fabrication from transition metal compounds are highly efficient oxygen evolution reaction (OER) electrocatalysts but face limits from adsorption energy scaling relationship and sluggish deprotonation kinetics. Herein, we present Fe-doped nickel hydrogen cyanamide (NiFe-HC), which is rapidly surface reconstructed into NiFe(OOH)-HC after OER. In-situ Raman spectroscopy and density functional theory (DFT) calculations, revealed that under OER conditions, -HNCN- converts into -NCN- ligand incorporating its abundant and uniform distribution across the active sites. DFT calculations further indicate that Fe predominantly acts as the active site, with -NCN- ligands contribute to the OER by facilitating the deprotonation of *OH in the rate-determining step (RDS), acting effectively as proton acceptor. The ensemble effect between Fe and -NCN- ligand forms the foundation of the exceptional electrocatalytic performance of NiFe(OOH)-HC (190 mV at 20 mA·cm). This discovery offers insights for designing innovative MOOH pre-catalysts to enhance OER efficiency.
由过渡金属化合物通过不可逆重构制造而成的金属氢氧化物（MOOH）是一种高效的氧进化反应（OER）电催化剂，但却面临着吸附能缩放关系和缓慢的去质子化动力学的限制。在此，我们提出了掺杂铁的氰氨化镍氢（NiFe-HC），它在 OER 后可迅速表面重构为 NiFe(OOH)-HC。原位拉曼光谱和密度泛函理论（DFT）计算显示，在 OER 条件下，-HNCN- 转化为 -NCN- 配体，并在活性位点上均匀分布。DFT 计算进一步表明，铁主要充当活性位点，而 -NCN- 配体则通过在速率决定步骤（RDS）中促进 *OH 的去质子化，有效地充当质子接受体，从而促进 OER。铁和-NCN-配体之间的集合效应是 NiFe(OOH)-HC（20 mA-cm 时电压为 190 mV）卓越电催化性能的基础。这一发现为设计创新的 MOOH 预催化剂以提高 OER 效率提供了启示。
{"title":"Rapid reconstruction of nickel iron hydrogen cyanamide with in-situ produced proton acceptor for efficient oxygen evolution","authors":"Muhammad Ajmal, Shishi Zhang, Xiaolei Guo, Xiaokang Liu, Chengxiang Shi, Ruijie Gao, Zhen-Feng Huang, Lun Pan, Xiangwen Zhang, Ji-Jun Zou","doi":"10.1016/j.apcatb.2024.124561","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124561","url":null,"abstract":"Metal oxyhydroxide (MOOH) through irreversible reconstructed fabrication from transition metal compounds are highly efficient oxygen evolution reaction (OER) electrocatalysts but face limits from adsorption energy scaling relationship and sluggish deprotonation kinetics. Herein, we present Fe-doped nickel hydrogen cyanamide (NiFe-HC), which is rapidly surface reconstructed into NiFe(OOH)-HC after OER. In-situ Raman spectroscopy and density functional theory (DFT) calculations, revealed that under OER conditions, -HNCN- converts into -NCN- ligand incorporating its abundant and uniform distribution across the active sites. DFT calculations further indicate that Fe predominantly acts as the active site, with -NCN- ligands contribute to the OER by facilitating the deprotonation of *OH in the rate-determining step (RDS), acting effectively as proton acceptor. The ensemble effect between Fe and -NCN- ligand forms the foundation of the exceptional electrocatalytic performance of NiFe(OOH)-HC (190 mV at 20 mA·cm). This discovery offers insights for designing innovative MOOH pre-catalysts to enhance OER efficiency.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142250050","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 : 2024-09-05DOI: 10.1016/j.apcatb.2024.124569
Zhiqiang Zhang, Yu Le, Lei Jing, Gongxun Huang, Jincan Kang, Qinghong Zhang, Ye Wang
The Fischer-Tropsch (FT) synthesis, characterized by its highly exothermic and high-throughput nature, traditionally yields a mix of C hydrocarbons and C1 by-products, which adversely affect carbon utilization efficiency. Herein, we design a Fe-foam structured catalyst to selectively produce high-value olefins in FT process. The Na-Zn-Fe/Fe-foam catalysts are prepared through a hydrothermal synthesis method, where the FeCO precursor is formed from Fe-foam, followed by addition of sodium and zinc modifiers. These catalysts achieve a remarkable olefin selectivity of ∼80 % and a space-time yield of ∼0.70 g g h at a CO conversion of 98 %, and further demonstrate outstanding stability. The structured catalysts, with expansive void volume and fully open network architecture, provide superior mass and heat transfer capabilities, and effectively mitigate the generation of CO and CH, offering a significant advantage in FT synthesis. This work presents a new strategy for the development of efficient catalysts in high exothermic catalytic reactions.
费托合成（FT）具有高放热和高通量的特点，传统上会产生 C 类烃类和 C1 类副产品的混合物，从而对碳的利用效率产生不利影响。在此，我们设计了一种铁泡沫结构催化剂，用于在傅立叶变换工艺中选择性地生产高价值烯烃。Na-Zn-Fe/Fe-foam 催化剂是通过水热合成法制备的，其中 FeCO 前驱体由 Fe-foam 生成，然后加入钠和锌改性剂。在一氧化碳转化率为 98% 的条件下，这些催化剂的烯烃选择性高达 ∼80 %，时空产率达∼0.70 g g h，而且具有出色的稳定性。这种结构催化剂空隙体积大，网络结构完全开放，具有优异的传质和传热能力，能有效减少 CO 和 CH 的生成，在 FT 合成中具有显著优势。这项工作为开发高放热催化反应中的高效催化剂提供了一种新策略。
{"title":"Foam-structured Fe catalysts for enhanced heat and mass transfer in synthesis of olefins from syngas","authors":"Zhiqiang Zhang, Yu Le, Lei Jing, Gongxun Huang, Jincan Kang, Qinghong Zhang, Ye Wang","doi":"10.1016/j.apcatb.2024.124569","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124569","url":null,"abstract":"The Fischer-Tropsch (FT) synthesis, characterized by its highly exothermic and high-throughput nature, traditionally yields a mix of C hydrocarbons and C1 by-products, which adversely affect carbon utilization efficiency. Herein, we design a Fe-foam structured catalyst to selectively produce high-value olefins in FT process. The Na-Zn-Fe/Fe-foam catalysts are prepared through a hydrothermal synthesis method, where the FeCO precursor is formed from Fe-foam, followed by addition of sodium and zinc modifiers. These catalysts achieve a remarkable olefin selectivity of ∼80 % and a space-time yield of ∼0.70 g g h at a CO conversion of 98 %, and further demonstrate outstanding stability. The structured catalysts, with expansive void volume and fully open network architecture, provide superior mass and heat transfer capabilities, and effectively mitigate the generation of CO and CH, offering a significant advantage in FT synthesis. This work presents a new strategy for the development of efficient catalysts in high exothermic catalytic reactions.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205088","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 inactive macromolecular substances would result in the membrane fouling and reduce the membrane flux in treating traditional Chinese medicine wastewater. Here, we report a novel photocatalytic membrane and utilize aloe-emodin (AE) as electron shuttle synergistically doped into Cu-FeOOH solid solution, then support the photocatalyst AE/Cu-FeOOH on PVDF membrane, which can effectively degrade tannic (95.69 %, 60 min). Furthermore, even after 6 hours of tannic solution filtration, the membrane maintains a high flux of 517 L m h bar. Combined with various spectral and photoelectric performance tests confirmed that AE/Cu-FeOOH-PVDF possesses high separation and transfer efficiency of photogenerated carriers. Meanwhile DFT calculation showed that the composite has better adsorption properties and HO activation ability. AE provided e to Cu-FeOOH, which accelerated the redox reaction process of Fe and Cu ions and produced more stable active free radicals to degrade tannic. This study provides a more environmentally friendly approach for utilizing photocatalytic membranes in the treatment of traditional Chinese medicine wastewater.
在处理中药废水时，非活性大分子物质会导致膜堵塞，降低膜通量。在此，我们报道了一种新型光催化膜，利用芦荟大黄素（AE）作为电子穿梭器协同掺杂到Cu-FeOOH固溶体中，然后将光催化剂AE/Cu-FeOOH支撑在PVDF膜上，可有效降解鞣酸（95.69%，60分钟）。此外，即使在单宁酸溶液过滤 6 小时后，膜仍能保持 517 L m h bar 的高通量。结合各种光谱和光电性能测试证实，AE/Cu-FeOOH-PVDF 具有很高的光生载流子分离和转移效率。同时，DFT 计算表明，该复合材料具有更好的吸附性能和 HO 活化能力。AE 为 Cu-FeOOH 提供了 e，从而加速了铁离子和铜离子的氧化还原反应过程，并产生了更稳定的活性自由基来降解单宁酸。这项研究为利用光催化膜处理中药废水提供了一种更环保的方法。
{"title":"The electron shuttle of aloe-emodin promotes the Cu-FeOOH solid solution photocatalytic membrane to activate hydrogen peroxide for the degradation of tannic in traditional Chinese medicine wastewater","authors":"Mengzhen Zhu, Jiajia Li, Manhua Chen, Yulu Liu, Qiong Mei, Hongbo Liu, Yuping Tang, Qizhao Wang","doi":"10.1016/j.apcatb.2024.124566","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124566","url":null,"abstract":"The inactive macromolecular substances would result in the membrane fouling and reduce the membrane flux in treating traditional Chinese medicine wastewater. Here, we report a novel photocatalytic membrane and utilize aloe-emodin (AE) as electron shuttle synergistically doped into Cu-FeOOH solid solution, then support the photocatalyst AE/Cu-FeOOH on PVDF membrane, which can effectively degrade tannic (95.69 %, 60 min). Furthermore, even after 6 hours of tannic solution filtration, the membrane maintains a high flux of 517 L m h bar. Combined with various spectral and photoelectric performance tests confirmed that AE/Cu-FeOOH-PVDF possesses high separation and transfer efficiency of photogenerated carriers. Meanwhile DFT calculation showed that the composite has better adsorption properties and HO activation ability. AE provided e to Cu-FeOOH, which accelerated the redox reaction process of Fe and Cu ions and produced more stable active free radicals to degrade tannic. This study provides a more environmentally friendly approach for utilizing photocatalytic membranes in the treatment of traditional Chinese medicine wastewater.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205085","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}
Identifying the spatial dynamic reconstruction of π-conjugated polymers for efficient carrier transport and controlling the intermediate process of the reaction are urgent and formidable challenges. In this study, a fresh perspective has emerged proposing to synergistically enhance the adaptability and resilience of dynamic torsion patterns in π-conjugated polymers to mediate charge separation and molecular activation. Excitingly, the highest flexible-robust structure and polarity of naphthalene-linked perylene diimide polymer (N-PDA) demonstrates a highest nitrate reduction rate of 5.36 mmol g h under light irradiation and ultrasonic condition, which is 7.5 times that of H-PDA. Theoretical calculations and experimental observations indicate that the strongest flexible-robust structure of N-PDA enhances the inclination of the rigid plane and atomic bond length, resulting in an accelerated uneven distribution of charges, molecular polarity, and electronic coupling to facilitate charge separation dynamics. Moreover, it exposes active sites that promote the adsorption and activation of NO ions while simultaneously regulating intermediate hydrogenation processes. Our study offers innovative prospects for enhancing catalytic efficiency through the implementation of spatial steric configuration of π-conjugated polymers.
确定π-共轭聚合物的空间动态重构以实现高效载流子传输并控制反应的中间过程是一项紧迫而艰巨的挑战。本研究提出了一个全新的视角，即协同增强π共轭聚合物动态扭转模式的适应性和弹性，以介导电荷分离和分子活化。令人兴奋的是，在光照射和超声波条件下，萘链过二亚胺聚合物（N-PDA）具有最高的柔性-稳健结构和极性，其硝酸盐还原率达到 5.36 mmol g h，是 H-PDA 的 7.5 倍。理论计算和实验观察结果表明，N-PDA 的柔性最强结构增强了刚性平面的倾斜度和原子键的长度，从而加速了电荷、分子极性和电子耦合的不均匀分布，促进了电荷分离动力学。此外，它还暴露了活性位点，这些位点可促进 NO 离子的吸附和活化，同时调节中间氢化过程。我们的研究为通过实施π共轭聚合物的空间立体构型来提高催化效率提供了创新前景。
{"title":"Synergistically flexible-robust effects mediate the dynamic reconfiguration of perylene diimide polymer to enhance piezo-photocatalytic nitrate reduction","authors":"Jiwen Zhang, Kailong Lv, Jinke Cheng, Yuhui Liu, Yi Wang, Shuang-Feng Yin, Peng Chen","doi":"10.1016/j.apcatb.2024.124558","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124558","url":null,"abstract":"Identifying the spatial dynamic reconstruction of π-conjugated polymers for efficient carrier transport and controlling the intermediate process of the reaction are urgent and formidable challenges. In this study, a fresh perspective has emerged proposing to synergistically enhance the adaptability and resilience of dynamic torsion patterns in π-conjugated polymers to mediate charge separation and molecular activation. Excitingly, the highest flexible-robust structure and polarity of naphthalene-linked perylene diimide polymer (N-PDA) demonstrates a highest nitrate reduction rate of 5.36 mmol g h under light irradiation and ultrasonic condition, which is 7.5 times that of H-PDA. Theoretical calculations and experimental observations indicate that the strongest flexible-robust structure of N-PDA enhances the inclination of the rigid plane and atomic bond length, resulting in an accelerated uneven distribution of charges, molecular polarity, and electronic coupling to facilitate charge separation dynamics. Moreover, it exposes active sites that promote the adsorption and activation of NO ions while simultaneously regulating intermediate hydrogenation processes. Our study offers innovative prospects for enhancing catalytic efficiency through the implementation of spatial steric configuration of π-conjugated polymers.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205086","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 : 2024-09-03DOI: 10.1016/j.apcatb.2024.124560
Kai Wang, Chuang Liu, Jingping Li, Qiang Cheng, Bin Liu, Jun Li
The construction of S-scheme heterojunctions effectively facilitates the spatial separation of photogenerated charge carriers for their involvement in photoreactions. However, the inefficient utilization of solar energy in these heterostructures is often due to unfavorable band-edge positions and suboptimal charge transport dynamics, which result in low photocatalytic efficiency when considering kinetic factors. In this study, sea urchin–like BiBrS/AgSiO S-scheme heterojunctions are fabricated, which exhibit excellent CO photoreduction performance under ultraviolet, visible, and near-infrared (NIR) light illumination. Experimental data and density functional theory calculations confirm the S-scheme charge transfer mechanisms, which enable the efficient separation of photogenerated carriers for CO reduction. Consequently, the optimized AgSiO/BiBrS heterostructures exhibit superior CO photoreduction activity under NIR light irradiation. This approach offers a strategy for designing advanced NIR-light-responsive photocatalysts for efficient CO photoreduction.
S 型异质结的构建可有效促进光生电荷载流子的空间分离，使其参与光反应。然而，这些异质结构对太阳能的利用效率不高，通常是由于带边位置不利和电荷传输动力学不理想，从而导致光催化效率低（考虑动力学因素）。本研究制备了海胆状 BiBrS/AgSiO S 型异质结，在紫外线、可见光和近红外（NIR）光照下表现出优异的 CO 光还原性能。实验数据和密度泛函理论计算证实了 S-梯度电荷转移机制，该机制能够有效分离光生载流子，从而实现 CO 还原。因此，优化的 AgSiO/BiBrS 异质结构在近红外光照射下表现出卓越的一氧化碳光还原活性。这种方法为设计先进的近红外光响应光催化剂以实现高效的 CO 光还原提供了一种策略。
{"title":"Near-infrared-responsive sea-urchin-like Ag6Si2O7/Bi19Br3S27 S-scheme heterojunction for efficient CO2 photoreduction","authors":"Kai Wang, Chuang Liu, Jingping Li, Qiang Cheng, Bin Liu, Jun Li","doi":"10.1016/j.apcatb.2024.124560","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124560","url":null,"abstract":"The construction of S-scheme heterojunctions effectively facilitates the spatial separation of photogenerated charge carriers for their involvement in photoreactions. However, the inefficient utilization of solar energy in these heterostructures is often due to unfavorable band-edge positions and suboptimal charge transport dynamics, which result in low photocatalytic efficiency when considering kinetic factors. In this study, sea urchin–like BiBrS/AgSiO S-scheme heterojunctions are fabricated, which exhibit excellent CO photoreduction performance under ultraviolet, visible, and near-infrared (NIR) light illumination. Experimental data and density functional theory calculations confirm the S-scheme charge transfer mechanisms, which enable the efficient separation of photogenerated carriers for CO reduction. Consequently, the optimized AgSiO/BiBrS heterostructures exhibit superior CO photoreduction activity under NIR light irradiation. This approach offers a strategy for designing advanced NIR-light-responsive photocatalysts for efficient CO photoreduction.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142226215","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 : 2024-09-03DOI: 10.1016/j.apcatb.2024.124563
Bo Kang, Zhilin Chen, Jie Yang, Mingxin Lv, Hongli He, Guoxin Chen, Liyuan Huai, Chunlin Chen, Jian Zhang
Balancing the Cu/Cu ratio is a common strategy to improve catalytic activity of Cu-based catalysts but is still constrained by low atomic utilization and the inherent nature of charge distribution. Herein, we reported a strategy of replacing the Cu active sites in Cu-based catalysts by constructing bimetallic sites on ceria, which consist of spatially separated trace amounts of palladium metal and plate-shaped Cu clusters with one-atom layers. The catalytic activity of the prepared CuPd/CeO-FA catalyst (using formic acid) was 4 times that of conventional CuPd/CeO-H catalyst in selective hydrogenation of 5-hydroxymethylfurfural to 2,5-bis(hydroxymethyl)furan, even outperforming some existing noble metal catalysts. Multiple characterizations and theoretical calculations demonstrated that the Pd atom is the heterolytic activation site for H molecules while plate-shaped Cu metal clusters act as effective hydrogenation places. This directional control involving both spatial relationship and electronic structure of the active site provides a new strategy for designing hydrogenated catalysts.
{"title":"Boosting hydrogenation properties of supported Cu-based catalysts by replacing Cu0 active sites","authors":"Bo Kang, Zhilin Chen, Jie Yang, Mingxin Lv, Hongli He, Guoxin Chen, Liyuan Huai, Chunlin Chen, Jian Zhang","doi":"10.1016/j.apcatb.2024.124563","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124563","url":null,"abstract":"Balancing the Cu/Cu ratio is a common strategy to improve catalytic activity of Cu-based catalysts but is still constrained by low atomic utilization and the inherent nature of charge distribution. Herein, we reported a strategy of replacing the Cu active sites in Cu-based catalysts by constructing bimetallic sites on ceria, which consist of spatially separated trace amounts of palladium metal and plate-shaped Cu clusters with one-atom layers. The catalytic activity of the prepared CuPd/CeO-FA catalyst (using formic acid) was 4 times that of conventional CuPd/CeO-H catalyst in selective hydrogenation of 5-hydroxymethylfurfural to 2,5-bis(hydroxymethyl)furan, even outperforming some existing noble metal catalysts. Multiple characterizations and theoretical calculations demonstrated that the Pd atom is the heterolytic activation site for H molecules while plate-shaped Cu metal clusters act as effective hydrogenation places. This directional control involving both spatial relationship and electronic structure of the active site provides a new strategy for designing hydrogenated catalysts.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205128","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 : 2024-09-03DOI: 10.1016/j.apcatb.2024.124562
Xuechao Tan, Suk Bong Hong
Natural gas engines are the most viable alternative to diesel and gasoline ones. However, the current state-of-art catalyst, palladium (Pd) on alumina, for eliminating unburnt methane from engine exhaust suffers from high light-off temperature (> 400 °C) and poor water tolerance. Here we systematically investigated the effects of zeolite structure and Si/Al ratio, catalyst calcination temperature and extra-framework cation type on catalytic performance of zeolite-supported Pd catalysts for wet methane combustion to overcome these limitations. We found that a 3.0 wt% Pd catalyst supported on Na-post-exchanged 500 °C-calcined IWV zeolite with a Si/Al ratio of 45 has a light-off temperature as low as 290 °C for methane combustion in the presence of 10 % water vapor while maintaining ca. 85 % methane conversion at 330 °C for 100 h. This study provides a new direction for bringing supported Pd catalysts close to real-world applications.
天然气发动机是柴油和汽油发动机最可行的替代品。然而，目前用于消除发动机尾气中未燃烧甲烷的最先进催化剂--氧化铝上的钯（Pd）--存在着点火温度高（> 400 °C）和耐水性差的问题。在此，我们系统地研究了沸石结构和硅/铝比例、催化剂煅烧温度和框架外阳离子类型对湿法甲烷燃烧沸石支撑钯催化剂催化性能的影响，以克服这些局限性。我们发现，在 Si/Al 比率为 45 的 Na 后置换 500 °C 煅烧 IWV 沸石上支撑的 3.0 wt% Pd 催化剂，在 10% 水蒸汽存在下燃烧甲烷的熄灭温度低至 290 °C，同时在 330 °C 下 100 小时内保持约 85% 的甲烷转化率。这项研究为使支撑钯催化剂接近实际应用提供了新的方向。
{"title":"A highly active and stable palladium zeolite catalyst for wet methane combustion","authors":"Xuechao Tan, Suk Bong Hong","doi":"10.1016/j.apcatb.2024.124562","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124562","url":null,"abstract":"Natural gas engines are the most viable alternative to diesel and gasoline ones. However, the current state-of-art catalyst, palladium (Pd) on alumina, for eliminating unburnt methane from engine exhaust suffers from high light-off temperature (> 400 °C) and poor water tolerance. Here we systematically investigated the effects of zeolite structure and Si/Al ratio, catalyst calcination temperature and extra-framework cation type on catalytic performance of zeolite-supported Pd catalysts for wet methane combustion to overcome these limitations. We found that a 3.0 wt% Pd catalyst supported on Na-post-exchanged 500 °C-calcined IWV zeolite with a Si/Al ratio of 45 has a light-off temperature as low as 290 °C for methane combustion in the presence of 10 % water vapor while maintaining ca. 85 % methane conversion at 330 °C for 100 h. This study provides a new direction for bringing supported Pd catalysts close to real-world applications.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205084","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 : 2024-09-02DOI: 10.1016/j.apcatb.2024.124556
Yuekun Hu, Mingwang Lu, Guanhua Zhang, Xiaowei Zhao, Yan Liu, Xiaojing Yang, Xiaofei Yu, Xinghua Zhang, Zunming Lu, Lanlan Li
Developing efficient and durable Pt-based electrocatalysts for oxygen reduction reaction (ORR) is critical for the practical application of fuel cells but still remains challenge at present. Here we successfully synthesized a series of ternary L1-PtCoFe (x=0.33, 0.50 and 0.67) intermetallic nanoparticles (NPs) supported on reduced graphene oxide for ORR catalysis. L1-PtCoFe exhibits the highest mass activity (MA) of 0.93 A mg at 0.9 V (1.82 times the corresponding binary L1-PtCo intermetallics) and minimal activity loss (24.73 % loss in MA) after 30,000 potential cycles. By Density Functional Theory calculations, the excellent performance of ternary L1-PtCoFe can be ascribed to: (1) more efficient electronic structure regulation caused by dual-element driven electron transfer, which leads to more electron accumulation on Pt and weakens the over-binding of oxygen-containing species, (2) the unique two-center bridge pattern of O adsorption over Pt-Fe site leads to ORR proceeding the dissociative mechanism, avoiding the formation of OOH*.
{"title":"Ternary ordered L10-Pt-Co-Fe intermetallics for efficient ORR catalysis through dissociation pathway","authors":"Yuekun Hu, Mingwang Lu, Guanhua Zhang, Xiaowei Zhao, Yan Liu, Xiaojing Yang, Xiaofei Yu, Xinghua Zhang, Zunming Lu, Lanlan Li","doi":"10.1016/j.apcatb.2024.124556","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124556","url":null,"abstract":"Developing efficient and durable Pt-based electrocatalysts for oxygen reduction reaction (ORR) is critical for the practical application of fuel cells but still remains challenge at present. Here we successfully synthesized a series of ternary L1-PtCoFe (x=0.33, 0.50 and 0.67) intermetallic nanoparticles (NPs) supported on reduced graphene oxide for ORR catalysis. L1-PtCoFe exhibits the highest mass activity (MA) of 0.93 A mg at 0.9 V (1.82 times the corresponding binary L1-PtCo intermetallics) and minimal activity loss (24.73 % loss in MA) after 30,000 potential cycles. By Density Functional Theory calculations, the excellent performance of ternary L1-PtCoFe can be ascribed to: (1) more efficient electronic structure regulation caused by dual-element driven electron transfer, which leads to more electron accumulation on Pt and weakens the over-binding of oxygen-containing species, (2) the unique two-center bridge pattern of O adsorption over Pt-Fe site leads to ORR proceeding the dissociative mechanism, avoiding the formation of OOH*.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205111","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}
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