Molecular Catalysis最新文献

Synergistic heterogeneous catalysis: MoS2/α-FeOOH nanocomposites for pH-universal PMS activation and efficient antibiotic degradation

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-04-23 DOI: 10.1016/j.mcat.2025.115150

Yuanyuan Tao , Yuemeng Duan , Zhiang Chen , Meng Ye , Zhixin Wang , Jianjian Yi , Wei Jiang , Binxian Gu , Fu Yang , Qingsong Hu

The development of high-efficiency catalysts for advanced oxidation processes is crucial for environmental remediation. In this study, a novel α-FeOOH/MoS₂ heterojunction catalyst was designed to address the intrinsic limitations of Fe-based materials in peroxymonosulfate (PMS) activation. By integrating MoS₂ nanoflowers with α-FeOOH nanorods, the nanocomposite catalyst exhibited an expanded specific surface area and improved interfacial charge transfer, facilitating accelerated redox cycling between Mo(IV/VI) and Fe(II/III) species. This synergistic interaction significantly enhanced PMS activation efficiency, enabling the near-complete degradation (∼99 %) of tetracycline (TC) within 30 min. The reaction rate was notably amplified, surpassing the performance of individual α-FeOOH and MoS₂ components by factors of 9.7 and 21.6, respectively. Moreover, the nanocomposite catalyst demonstrated robust degradation performance across a broad pH range (3–11) and maintained high efficiency under varying PMS dosages and pollutant concentrations. Mechanistic investigations through electron spin resonance (ESR) and radical quenching experiments confirmed the involvement of multiple reactive species, including sulfate radicals (SO₄^•−), superoxide radicals (O₂^•−), hydroxyl radicals (•OH), and singlet oxygen (¹O₂). These findings highlight the potential of α-FeOOH/MoS₂ heterojunctions as advanced, sustainable catalysts for wastewater treatment and environmental purification.

{"title":"Synergistic heterogeneous catalysis: MoS2/α-FeOOH nanocomposites for pH-universal PMS activation and efficient antibiotic degradation","authors":"Yuanyuan Tao , Yuemeng Duan , Zhiang Chen , Meng Ye , Zhixin Wang , Jianjian Yi , Wei Jiang , Binxian Gu , Fu Yang , Qingsong Hu","doi":"10.1016/j.mcat.2025.115150","DOIUrl":"10.1016/j.mcat.2025.115150","url":null,"abstract":"<div><div>The development of high-efficiency catalysts for advanced oxidation processes is crucial for environmental remediation. In this study, a novel α-FeOOH/MoS2 heterojunction catalyst was designed to address the intrinsic limitations of Fe-based materials in peroxymonosulfate (PMS) activation. By integrating MoS2 nanoflowers with α-FeOOH nanorods, the nanocomposite catalyst exhibited an expanded specific surface area and improved interfacial charge transfer, facilitating accelerated redox cycling between Mo(IV/VI) and Fe(II/III) species. This synergistic interaction significantly enhanced PMS activation efficiency, enabling the near-complete degradation (∼99 %) of tetracycline (TC) within 30 min. The reaction rate was notably amplified, surpassing the performance of individual α-FeOOH and MoS2 components by factors of 9.7 and 21.6, respectively. Moreover, the nanocomposite catalyst demonstrated robust degradation performance across a broad pH range (3–11) and maintained high efficiency under varying PMS dosages and pollutant concentrations. Mechanistic investigations through electron spin resonance (ESR) and radical quenching experiments confirmed the involvement of multiple reactive species, including sulfate radicals (SO4•−), superoxide radicals (O2•−), hydroxyl radicals (•OH), and singlet oxygen (1O2). These findings highlight the potential of α-FeOOH/MoS2 heterojunctions as advanced, sustainable catalysts for wastewater treatment and environmental purification.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"581 ","pages":"Article 115150"},"PeriodicalIF":3.9,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858764","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Bimetallic synergy in Si-(CH₂)ₙ-Si-bridged binuclear indenyl-pyrrolidinyl titanium catalysts for ethylene/1-octene copolymerization

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-04-22 DOI: 10.1016/j.mcat.2025.115145

Xiangsheng Mu, Fengxin Yang, Qishun Guo, Yu Zhang, Yanhui Chen, Tao Jiang

To investigate the cooperative effect of binuclear metallocene catalysts in olefin polymerization, a series of Si-(CH₂)ₙ-Si bridged binuclear indene pyrrolidine titanium catalysts 2d-7d (Ti₂) were synthesized. The mononuclear complex NC₄H₈CpC₆H₄(Me)₂SiN(CH₃)₃TiCl₂ (Ti₁) was also prepared for control experiments. DFT calculations show that increasing the methylene spacer length (n=2–7) simultaneously enlarges the Ti-Ti distance (8.93–14.65 Å) and reduces the buried volume (%Vbur=16.2–12.4 %). In the presence of [Ph₃C][B(C₆F₅)₄] as a co-catalyst, 2d-7d (Ti₂) showed higher activity and thermal stability. For ethylene/1-octene copolymers, especially 5d (Ti₂) at 120 °C, the activity was 2.65×10⁷ g/(mol·h), the Mw was 66.93×10⁴ g/mol, and the 1-octene insertion rate was 8.4 mol%, which were 1.8 times, 1.9 times, and 1.3 times higher than that of mononuclear 1d (Ti₁), respectively. Copolymers from binuclear catalysts showed reduced crystallinity and melting points due to enhanced branching, alongside improved tensile strength and elastic recovery.

为了研究双核茂金属催化剂在烯烃聚合中的协同效应，合成了一系列 Si-(CH₂)ₙ-Si桥接双核茚吡咯烷钛催化剂 2d-7d (Ti2)。同时还制备了单核络合物 NC₄H₈CpC₆H₄(Me)₂SiN(CH₃)₃TiCl2（Ti1）作为对照实验。DFT 计算表明，增加亚甲基间隔长度（n=2-7）可同时扩大钛-钛距离（8.93-14.65 Å）并减少埋藏体积（%Vbur=16.2-12.4 %）。在[Ph3C][B(C6F5)4]作为助催化剂的情况下，2d-7d (Ti2) 表现出更高的活性和热稳定性。对于乙烯/1-辛烯共聚物，尤其是 5d (Ti2)，在 120 ℃ 时的活性为 2.65×107 g/(mol-h)，Mw 为 66.93×104 g/mol，1-辛烯插入率为 8.4 mol%，分别是单核 1d (Ti1) 的 1.8 倍、1.9 倍和 1.3 倍。双核催化剂产生的共聚物由于支化增强而降低了结晶度和熔点，同时还提高了拉伸强度和弹性恢复能力。

{"title":"Bimetallic synergy in Si-(CH₂)ₙ-Si-bridged binuclear indenyl-pyrrolidinyl titanium catalysts for ethylene/1-octene copolymerization","authors":"Xiangsheng Mu, Fengxin Yang, Qishun Guo, Yu Zhang, Yanhui Chen, Tao Jiang","doi":"10.1016/j.mcat.2025.115145","DOIUrl":"10.1016/j.mcat.2025.115145","url":null,"abstract":"<div><div>To investigate the cooperative effect of binuclear metallocene catalysts in olefin polymerization, a series of Si-(CH₂)ₙ-Si bridged binuclear indene pyrrolidine titanium catalysts 2d-7d (Ti2) were synthesized. The mononuclear complex NC₄H₈CpC₆H₄(Me)₂SiN(CH₃)₃TiCl2 (Ti1) was also prepared for control experiments. DFT calculations show that increasing the methylene spacer length (n=2–7) simultaneously enlarges the Ti-Ti distance (8.93–14.65 Å) and reduces the buried volume (%Vbur=16.2–12.4 %). In the presence of [Ph3C][B(C6F5)4] as a co-catalyst, 2d-7d (Ti2) showed higher activity and thermal stability. For ethylene/1-octene copolymers, especially 5d (Ti2) at 120 °C, the activity was 2.65×107 g/(mol·h), the Mw was 66.93×104 g/mol, and the 1-octene insertion rate was 8.4 mol%, which were 1.8 times, 1.9 times, and 1.3 times higher than that of mononuclear 1d (Ti1), respectively. Copolymers from binuclear catalysts showed reduced crystallinity and melting points due to enhanced branching, alongside improved tensile strength and elastic recovery.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"581 ","pages":"Article 115145"},"PeriodicalIF":3.9,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143854571","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Defect-engineered CuxO/CeO2 catalysts: Enhanced low-temperature CO preferential oxidation through dual-promotion of CO adsorption and O2 activation

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-04-22 DOI: 10.1016/j.mcat.2025.115148

Changjin Xu , Jiuyang Wang , Desheng Wang , Herima Qi , Laibing Wang , Riqing Cheng , Na Ta , Jiahao Shi , Wenyao Zhang , Jianping Chen , Junfang Ding , Huiqing Guo

The preferential oxidation of CO (CO-PROX) represents a critical strategy for trace CO elimination in hydrogen purification, where CO adsorption and O₂ activation are crucial for enhancing catalytic performance. Herein, we report a defect-engineered strategy mediated by MOF to promote CO adsorption and O₂ activation. By pyrolyzing Ce-BDC MOF, we synthesized CeO₂–O support with a high–density mesoporous structure and high surface area, facilitating the well-dispersion of CuₓO species and forming abundant interfacial Cu⁺ active sites. The well-dispersed Cu_xO species enhance their interaction with CeO₂–O, resulting in weakened Ce–O bonds and promoting both lattice oxygen activation and oxygen vacancy (Vo) formation for enhanced O₂ activation. The optimized 15Cu_xO/CeO₂–O catalyst demonstrates exceptional catalytic efficiency, achieving complete CO conversion at a comparatively low temperature (T₁₀₀ _% = 115 °C), coupled with broad temperature window applicability and outstanding stability over multiple cycles. This work establishes a MOF-guided paradigm for engineering multifunctional catalytic sites, offering a generalizable approach to design high-performance oxide catalysts for hydrogen purification and beyond.

{"title":"Defect-engineered CuxO/CeO2 catalysts: Enhanced low-temperature CO preferential oxidation through dual-promotion of CO adsorption and O2 activation","authors":"Changjin Xu , Jiuyang Wang , Desheng Wang , Herima Qi , Laibing Wang , Riqing Cheng , Na Ta , Jiahao Shi , Wenyao Zhang , Jianping Chen , Junfang Ding , Huiqing Guo","doi":"10.1016/j.mcat.2025.115148","DOIUrl":"10.1016/j.mcat.2025.115148","url":null,"abstract":"<div><div>The preferential oxidation of CO (CO-PROX) represents a critical strategy for trace CO elimination in hydrogen purification, where CO adsorption and O2 activation are crucial for enhancing catalytic performance. Herein, we report a defect-engineered strategy mediated by MOF to promote CO adsorption and O2 activation. By pyrolyzing Ce-BDC MOF, we synthesized CeO2–O support with a high–density mesoporous structure and high surface area, facilitating the well-dispersion of CuₓO species and forming abundant interfacial Cu+ active sites. The well-dispersed CuxO species enhance their interaction with CeO2–O, resulting in weakened Ce–O bonds and promoting both lattice oxygen activation and oxygen vacancy (Vo) formation for enhanced O2 activation. The optimized 15CuxO/CeO2–O catalyst demonstrates exceptional catalytic efficiency, achieving complete CO conversion at a comparatively low temperature (T100 % = 115 °C), coupled with broad temperature window applicability and outstanding stability over multiple cycles. This work establishes a MOF-guided paradigm for engineering multifunctional catalytic sites, offering a generalizable approach to design high-performance oxide catalysts for hydrogen purification and beyond.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"581 ","pages":"Article 115148"},"PeriodicalIF":3.9,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143854570","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

The Influence of In-modified NiMoS active phase on the direct desulfurization reaction process of 4,6-Dimethyldibenzothiophene

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-04-22 DOI: 10.1016/j.mcat.2025.115143

Xinmeng Zhang , Xu Cheng , Jie Kang , Fei Fan , Houxiang Sun , Anning Zhou , Zhiping Chen , Huabing Zhang , Yingfeng Duan , Lina Wang , Wenwu Zhou

Presently, the number of corner active site of formed NiMoS active phase, which is supported on non-precious metal hydrodesulfurization (HDS) catalyst, is limited and its ductility is poor, greatly reducing direct·desulfurization (DDS) and HDS performances, which brings great challenges to ultra-deep desulfurization. Herein, we used the density functional theory calculation method to explore the effect of single-atom In promoter on geometric and electron structures of active phase, investigated adsorption behaviors of 4,6-dimethyldibenzothiophene (4,6-DMDBT) at different active sites, and thoroughly clarified the effect of these changes on the 4,6-DMDBT DDS pathway. The results indicate that established single-atom In-doped InNiMoS model shown electron-rich characteristic. It was due to strongly s-p-d orbitals interaction of In-Ni atomic pairs loaded at long Mo-edge creating a new active site (E-1) with activity similar to the corner active site. Moreover, doped-In atom at short S-edge improved ductility of the corner active site and effectively increased its geometry space. At the corner active site, first C-S bond cleavage was still rate-controlling step (RCS) of the 4,6-DMDBT DDS, but obtained barriers were different due to the effect of activating H radical by the single-atom In promoter loaded at the short S-edge active site. At the formed E-1 active site of the long Mo-edge active site, the RCS barrier of the 4,6-DMDBT DDS significantly decreased from 201.60 to 140.44 kJ·mol^-1, successfully achieving 4,6-DMDBT DDS conversion.

{"title":"The Influence of In-modified NiMoS active phase on the direct desulfurization reaction process of 4,6-Dimethyldibenzothiophene","authors":"Xinmeng Zhang , Xu Cheng , Jie Kang , Fei Fan , Houxiang Sun , Anning Zhou , Zhiping Chen , Huabing Zhang , Yingfeng Duan , Lina Wang , Wenwu Zhou","doi":"10.1016/j.mcat.2025.115143","DOIUrl":"10.1016/j.mcat.2025.115143","url":null,"abstract":"<div><div>Presently, the number of corner active site of formed NiMoS active phase, which is supported on non-precious metal hydrodesulfurization (HDS) catalyst, is limited and its ductility is poor, greatly reducing direct·desulfurization (DDS) and HDS performances, which brings great challenges to ultra-deep desulfurization. Herein, we used the density functional theory calculation method to explore the effect of single-atom In promoter on geometric and electron structures of active phase, investigated adsorption behaviors of 4,6-dimethyldibenzothiophene (4,6-DMDBT) at different active sites, and thoroughly clarified the effect of these changes on the 4,6-DMDBT DDS pathway. The results indicate that established single-atom In-doped InNiMoS model shown electron-rich characteristic. It was due to strongly s-p-d orbitals interaction of In-Ni atomic pairs loaded at long Mo-edge creating a new active site (E-1) with activity similar to the corner active site. Moreover, doped-In atom at short S-edge improved ductility of the corner active site and effectively increased its geometry space. At the corner active site, first C-S bond cleavage was still rate-controlling step (RCS) of the 4,6-DMDBT DDS, but obtained barriers were different due to the effect of activating H radical by the single-atom In promoter loaded at the short S-edge active site. At the formed E-1 active site of the long Mo-edge active site, the RCS barrier of the 4,6-DMDBT DDS significantly decreased from 201.60 to 140.44 kJ·mol-1, successfully achieving 4,6-DMDBT DDS conversion.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"581 ","pages":"Article 115143"},"PeriodicalIF":3.9,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143854572","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Photosensitization of transition metal chalcogenide with metal nanoclusters for boosted photocatalysis

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-04-22 DOI: 10.1016/j.mcat.2025.115149

Huawei Xie , Junyi Zhang , Guangcan Xiao , Fang-Xing Xiao

Metal nanoclusters (NCs), characterized by the merits of unique stacking structure, quantum confinement effect, and abundant active centers, have garnered enormous attention in photocatalysis. However, inherent instability, fast carrier recombination, and complex interfacial charge transport mechanism of metal NCs remain the core challenges, thereby refraining their wide-spread applications in heterogeneous photocatalysis. In this work, tailor-made L-glutathione reduced (GSH) protected Au₂₂(GSH)₁₈ NCs are anchored on the transition metal chalcogenide (CdS) for constructing CdS/Au₂₂(GSH)₁₈ heterostructure artificial photosystems by a self-assembly approach. The CdS/Au₂₂(GSH)₁₈ nanocomposite exhibits the improved visible-light-driven photoactivity for reduction of aromatic nitro compounds compared with single counterpart. This is mainly attributed to the pivotal role of Au₂₂(GSH)₁₈ NCs as visible-light-absorbing antennas and the suitable energy level alignment between Au₂₂(GSH)₁₈ NCs and CdS, considerably improving the charge migration and separation efficiency and thereby enhancing the photocatalytic performances. Our investigation provides enriched information on the charge transport mechanism of metal NCs in photoredox organic transformation.

{"title":"Photosensitization of transition metal chalcogenide with metal nanoclusters for boosted photocatalysis","authors":"Huawei Xie , Junyi Zhang , Guangcan Xiao , Fang-Xing Xiao","doi":"10.1016/j.mcat.2025.115149","DOIUrl":"10.1016/j.mcat.2025.115149","url":null,"abstract":"<div><div>Metal nanoclusters (NCs), characterized by the merits of unique stacking structure, quantum confinement effect, and abundant active centers, have garnered enormous attention in photocatalysis. However, inherent instability, fast carrier recombination, and complex interfacial charge transport mechanism of metal NCs remain the core challenges, thereby refraining their wide-spread applications in heterogeneous photocatalysis. In this work, tailor-made L-glutathione reduced (GSH) protected Au22(GSH)18 NCs are anchored on the transition metal chalcogenide (CdS) for constructing CdS/Au22(GSH)18 heterostructure artificial photosystems by a self-assembly approach. The CdS/Au22(GSH)18 nanocomposite exhibits the improved visible-light-driven photoactivity for reduction of aromatic nitro compounds compared with single counterpart. This is mainly attributed to the pivotal role of Au22(GSH)18 NCs as visible-light-absorbing antennas and the suitable energy level alignment between Au22(GSH)18 NCs and CdS, considerably improving the charge migration and separation efficiency and thereby enhancing the photocatalytic performances. Our investigation provides enriched information on the charge transport mechanism of metal NCs in photoredox organic transformation.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"581 ","pages":"Article 115149"},"PeriodicalIF":3.9,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143854573","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Frustrated Lewis pairs promote selective methane oxidation over ZSM-5 supported Au-WO3 photocatalyst

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-04-21 DOI: 10.1016/j.mcat.2025.115141

Tong Wu , Mengyao Zhang , Xiaoxiao Gong , Caihong Ni , Yupeng Zou , Panpan Gao , Songmei Sun

Selective oxidation of methane to high value-added chemicals by artificial photosynthesis offers an energy-efficient strategy for the sustainable chemical industry. However, activation of CH₄ remains a great challenge due to the inert CH bond, bringing on a low efficiency and selectivity of high-valued oxygenate product, which limits the commercial application of this technology. Herein, frustrated Lewis pairs (FLPs) as active sites were precisely fabricated over Au-WO₃ loaded ZSM-5 (AuW-ZSM-5) catalysts for the activation of CH₄. Compared to other samples, FLPs-enriched Au_0.1W_0.58-ZSM-5 enable the efficient additive-free selective CH₄ oxidation to high valued oxygenate liquid product (CH₃OH, HCOOH, CH₃COOH) with a yield of up to 139.72 µmol g^-1 h^-1 and a selectivity of 98.2 %. In-situ DRIFT and EPR studies revealed the mechanism and approach of CH₄ activation by FLPs on the AuW-ZSM-5 catalyst. It was found owing to steric encumbrance FLPs facilitate the generation of weakly bonded ·CH₃ and ·OH radicals from water dissociation and methane activation under simulated solar light, which then significantly improved the generation of primary oxygenate liquid product by radical reactions and suppress over oxidation. This finding provides new insight into the construction of FLPs and a new perspective on the activation of CH₄.

{"title":"Frustrated Lewis pairs promote selective methane oxidation over ZSM-5 supported Au-WO3 photocatalyst","authors":"Tong Wu , Mengyao Zhang , Xiaoxiao Gong , Caihong Ni , Yupeng Zou , Panpan Gao , Songmei Sun","doi":"10.1016/j.mcat.2025.115141","DOIUrl":"10.1016/j.mcat.2025.115141","url":null,"abstract":"<div><div>Selective oxidation of methane to high value-added chemicals by artificial photosynthesis offers an energy-efficient strategy for the sustainable chemical industry. However, activation of CH4 remains a great challenge due to the inert C<img>H bond, bringing on a low efficiency and selectivity of high-valued oxygenate product, which limits the commercial application of this technology. Herein, frustrated Lewis pairs (FLPs) as active sites were precisely fabricated over Au-WO3 loaded ZSM-5 (AuW-ZSM-5) catalysts for the activation of CH4. Compared to other samples, FLPs-enriched Au0.1W0.58-ZSM-5 enable the efficient additive-free selective CH4 oxidation to high valued oxygenate liquid product (CH3OH, HCOOH, CH3COOH) with a yield of up to 139.72 µmol g-1 h-1 and a selectivity of 98.2 %. In-situ DRIFT and EPR studies revealed the mechanism and approach of CH4 activation by FLPs on the AuW-ZSM-5 catalyst. It was found owing to steric encumbrance FLPs facilitate the generation of weakly bonded ·CH3 and ·OH radicals from water dissociation and methane activation under simulated solar light, which then significantly improved the generation of primary oxygenate liquid product by radical reactions and suppress over oxidation. This finding provides new insight into the construction of FLPs and a new perspective on the activation of CH4.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"581 ","pages":"Article 115141"},"PeriodicalIF":3.9,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143855025","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

N, S coordination in Co single atom catalyst promoting CO2RR towards HCOOH at negative potentials

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-04-21 DOI: 10.1016/j.mcat.2025.115137

Huashuo Zhang , Maohuai Wang , Shoufu Cao , Zengxuan Chen , Siyuan Liu , Hongyu Chen , Yitong Yin , Zhaolong Yue , Shuxian Wei , Zhaojie Wang , Xiaoqing Lu

Co-based single-atom catalysts (Co-SACs) have attracted widespread attention in electrocatalytic CO₂ reduction reaction (CO₂RR). The coordination environment around Co active centers plays a crucial role in determining their intrinsic catalytic activity. This work systematically investigates the effect of introducing different numbers of S atoms into the Co-N₄ coordination environment (Co-N_xS_4-x, x = 1––4) on the CO₂RR performance at negative potentials. Among all structures, para-sulfur doped structure (p-CoN₂S₂) performs best with the limiting potentials for HCOOH generation of –0.19, 0, and 0 V at –0.23, –0.54, and –0.84 V, respectively. Compared to CoN₄, the substitution of S atoms in p-CoN₂S₂ results in the emergence of two electron distribution peaks at –0.46 and –0.02 eV, primarily contributed by the Co

d_{yz}

and

d_{xz}

orbitals. This significantly reduces the band gap of p-CoN₂S₂ to 0.36 eV, much lower than that of CoN₄ (1.82 eV), thereby enhancing the electrical conductivity. Additionally, p-CoN₂S₂ exhibits a higher occupation of the Co

d_{z^{2}}

orbital, which is beneficial for the electron transfer from Co atom to CO₂, thus promoting CO₂RR. This work highlights p-CoN₂S₂ as an efficient catalyst for HCOOH production, and demonstrates that the N, S coordination is an effective strategy to modulate the CO₂RR performance at negative potentials.

{"title":"N, S coordination in Co single atom catalyst promoting CO2RR towards HCOOH at negative potentials","authors":"Huashuo Zhang , Maohuai Wang , Shoufu Cao , Zengxuan Chen , Siyuan Liu , Hongyu Chen , Yitong Yin , Zhaolong Yue , Shuxian Wei , Zhaojie Wang , Xiaoqing Lu","doi":"10.1016/j.mcat.2025.115137","DOIUrl":"10.1016/j.mcat.2025.115137","url":null,"abstract":"<div><div>Co-based single-atom catalysts (Co-SACs) have attracted widespread attention in electrocatalytic CO2 reduction reaction (CO2RR). The coordination environment around Co active centers plays a crucial role in determining their intrinsic catalytic activity. This work systematically investigates the effect of introducing different numbers of S atoms into the Co-N4 coordination environment (Co-NxS4-x, x = 1––4) on the CO2RR performance at negative potentials. Among all structures, para-sulfur doped structure (p-CoN2S2) performs best with the limiting potentials for HCOOH generation of –0.19, 0, and 0 V at –0.23, –0.54, and –0.84 V, respectively. Compared to CoN4, the substitution of S atoms in p-CoN2S2 results in the emergence of two electron distribution peaks at –0.46 and –0.02 eV, primarily contributed by the Co <math><msub><mi>d</mi><mtext>yz</mtext></msub></math> and <math><msub><mi>d</mi><mtext>xz</mtext></msub></math> orbitals. This significantly reduces the band gap of p-CoN2S2 to 0.36 eV, much lower than that of CoN4 (1.82 eV), thereby enhancing the electrical conductivity. Additionally, p-CoN2S2 exhibits a higher occupation of the Co <math><msub><mi>d</mi><msup><mrow><mi>z</mi></mrow><mn>2</mn></msup></msub></math> orbital, which is beneficial for the electron transfer from Co atom to CO2, thus promoting CO2RR. This work highlights p-CoN2S2 as an efficient catalyst for HCOOH production, and demonstrates that the N, S coordination is an effective strategy to modulate the CO2RR performance at negative potentials.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"581 ","pages":"Article 115137"},"PeriodicalIF":3.9,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143851501","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Theoretical simulations inspired the design of Ni nanoparticles-NiN4 single atom composites for efficient CO2 electro-reduction at ultralow overpotential

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-04-19 DOI: 10.1016/j.mcat.2025.115125

Huan Wang , Shu-Wei Yin , Jianchuan Liu , Weitao Wang , Zhen-Hong He , Kuan Wang , Zhi-Hao Zhao , Zhao-Tie Liu

Ni, especially Ni single atom catalysts (SACs) are the most promising electrocatalyst in the reduction of CO₂ to CO. However, the high energy barrier for the formation of *COOH on Ni SA sites leads to a high overpotential for CO₂RR, which severely hinders the CO production efficiency. How the coupling effect of Ni SAs and Ni nanoparticles (NPs) sites improve the performance of Ni-based electrocatalysts is interesting to be investigated. Herein, theoretical calculations revealed that the synergy of Ni SAs and Ni NPs could efficiently lower the energy barrier of the *COOH formation via promoting the H₂O dissociation process to accelerate the *H supply for CO₂ protonation as well as promote the CO₂ adsorption and CO desorption, thus improving catalytic activity. Based on the theoretical study, Ni-N₄ SA coupled with Ni nanoparticles supported on nitrogen-doped carbon nanotubes (Ni-N₄Ni_NP/NCNT) was designed. As electrocatalyst, the Ni-N₄Ni_NP/NCNT showed an ultralow onset overpotential of 60 mV for CO₂RR-to-CO, and achieves a FE_CO of ∼99 % from an overpotential of as low as 160 mV, outperforming state-of-the-art Ni SACs. This work not only sheds new light for the rational synthesis of Ni-based catalysts with both Ni SAs and Ni NPs sites to achieve efficient CO₂RR to CO, but also offers an in-depth insight for the origin of efficient performance of cooperative Ni_SA-Ni_NP catalysts.

{"title":"Theoretical simulations inspired the design of Ni nanoparticles-NiN4 single atom composites for efficient CO2 electro-reduction at ultralow overpotential","authors":"Huan Wang , Shu-Wei Yin , Jianchuan Liu , Weitao Wang , Zhen-Hong He , Kuan Wang , Zhi-Hao Zhao , Zhao-Tie Liu","doi":"10.1016/j.mcat.2025.115125","DOIUrl":"10.1016/j.mcat.2025.115125","url":null,"abstract":"<div><div>Ni, especially Ni single atom catalysts (SACs) are the most promising electrocatalyst in the reduction of CO2 to CO. However, the high energy barrier for the formation of *COOH on Ni SA sites leads to a high overpotential for CO2RR, which severely hinders the CO production efficiency. How the coupling effect of Ni SAs and Ni nanoparticles (NPs) sites improve the performance of Ni-based electrocatalysts is interesting to be investigated. Herein, theoretical calculations revealed that the synergy of Ni SAs and Ni NPs could efficiently lower the energy barrier of the *COOH formation via promoting the H2O dissociation process to accelerate the *H supply for CO2 protonation as well as promote the CO2 adsorption and CO desorption, thus improving catalytic activity. Based on the theoretical study, Ni-N4 SA coupled with Ni nanoparticles supported on nitrogen-doped carbon nanotubes (Ni-N4<img>NiNP/NCNT) was designed. As electrocatalyst, the Ni-N4<img>NiNP/NCNT showed an ultralow onset overpotential of 60 mV for CO2RR-to-CO, and achieves a FECO of ∼99 % from an overpotential of as low as 160 mV, outperforming state-of-the-art Ni SACs. This work not only sheds new light for the rational synthesis of Ni-based catalysts with both Ni SAs and Ni NPs sites to achieve efficient CO2RR to CO, but also offers an in-depth insight for the origin of efficient performance of cooperative NiSA-NiNP catalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"580 ","pages":"Article 115125"},"PeriodicalIF":3.9,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143847830","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Electric field-enhanced hydrogenation catalysis: modified palladium-graphene oxide composites 电场增强氢化催化：改性钯-氧化石墨烯复合材料

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-04-19 DOI: 10.1016/j.mcat.2025.115132

Shi Wee Yee , Fazira Ilyana Abdul Razak , Suhaila Sapari , Hadi Nur , Ghozlan Elbashir Amer , Siti Salwa Alias

Palladium-graphene oxide (Pd-GO) composites show promise as catalysts for alkene hydrogenation, but challenges such as metal particle agglomeration and limited conductivity hinder their widespread use. In this study, Pd-GO and polyvinylpyrrolidone-stabilized Pd-GO (Pd-PVP/GO) composites were synthesized and characterized using FTIR, XRD, SEM, EDX, and HRTEM. The incorporation of PVP as a stabilizing and capping agent was found to significantly improve the dispersion an reduce agglomeration of Pd nanoparticles in Pd-PVP/GO. Catalytic performance evaluation in the hydrogenation of 1-octene under an external electric field (EEF) revealed enhanced activity for both composites, with Pd-GO showing the highest conversion efficiency. Computational studies further confirmed that the improved reactivity of Pd-GO is attributed to its smaller band gap and favourable electron density distribution upon addition of Pd. The synergistic effect between Pd-GO and EEF highlights the potential of electric field-assisted catalysis in alkene hydrogenation. this work provides valuable insights into the development of high-performance, sustainable catalysts for industrial hydrogenation processes.

{"title":"Electric field-enhanced hydrogenation catalysis: modified palladium-graphene oxide composites","authors":"Shi Wee Yee , Fazira Ilyana Abdul Razak , Suhaila Sapari , Hadi Nur , Ghozlan Elbashir Amer , Siti Salwa Alias","doi":"10.1016/j.mcat.2025.115132","DOIUrl":"10.1016/j.mcat.2025.115132","url":null,"abstract":"<div><div>Palladium-graphene oxide (Pd-GO) composites show promise as catalysts for alkene hydrogenation, but challenges such as metal particle agglomeration and limited conductivity hinder their widespread use. In this study, Pd-GO and polyvinylpyrrolidone-stabilized Pd-GO (Pd-PVP/GO) composites were synthesized and characterized using FTIR, XRD, SEM, EDX, and HRTEM. The incorporation of PVP as a stabilizing and capping agent was found to significantly improve the dispersion an reduce agglomeration of Pd nanoparticles in Pd-PVP/GO. Catalytic performance evaluation in the hydrogenation of 1-octene under an external electric field (EEF) revealed enhanced activity for both composites, with Pd-GO showing the highest conversion efficiency. Computational studies further confirmed that the improved reactivity of Pd-GO is attributed to its smaller band gap and favourable electron density distribution upon addition of Pd. The synergistic effect between Pd-GO and EEF highlights the potential of electric field-assisted catalysis in alkene hydrogenation. this work provides valuable insights into the development of high-performance, sustainable catalysts for industrial hydrogenation processes.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"580 ","pages":"Article 115132"},"PeriodicalIF":3.9,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143847826","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Bimetallic Co-Mn catalyzed chemselective oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-04-18 DOI: 10.1016/j.mcat.2025.115135

Rui Zhu , Fang Gao , Xinglong Li

The development of efficient catalysts for the stepwise oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformyl furan (DFF), 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), 5-Formyl-2-furancarboxylic acid (FFCA) or 2,5-furandicarboxylic acid (FDCA) is critical for biomass valorization. Herein, we reported a bimetallic Co-Mn catalyst anchored on nitrogen-doped porous carbon, which was used for the oxidation of HMF to FDCA, avoiding the use of high temperature and high-pressure oxygen. High FDCA selectivity (>95 %) was achieved through reaction condition optimization. And HMF→DFF→FFCA→FDCA was considered to be the main reaction pathway during the whole oxidation process. Additionally, the chemical environment of the constituent elements of the used catalyst was analyzed by XPS. TEM revealed that the catalyst retained its porous structure and excellent metal dispersion after the reaction. This structural stability was corroborated by sustained >90 % FDCA selectivity over five consecutive reaction cycles. This work established a dual-metal synergy strategy for multi-step oxidation pathways, offering insights into the design of robust catalysts for biomass-derived platform molecule upgrading.

{"title":"Bimetallic Co-Mn catalyzed chemselective oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid","authors":"Rui Zhu , Fang Gao , Xinglong Li","doi":"10.1016/j.mcat.2025.115135","DOIUrl":"10.1016/j.mcat.2025.115135","url":null,"abstract":"<div><div>The development of efficient catalysts for the stepwise oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformyl furan (DFF), 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), 5-Formyl-2-furancarboxylic acid (FFCA) or 2,5-furandicarboxylic acid (FDCA) is critical for biomass valorization. Herein, we reported a bimetallic Co-Mn catalyst anchored on nitrogen-doped porous carbon, which was used for the oxidation of HMF to FDCA, avoiding the use of high temperature and high-pressure oxygen. High FDCA selectivity (>95 %) was achieved through reaction condition optimization. And HMF→DFF→FFCA→FDCA was considered to be the main reaction pathway during the whole oxidation process. Additionally, the chemical environment of the constituent elements of the used catalyst was analyzed by XPS. TEM revealed that the catalyst retained its porous structure and excellent metal dispersion after the reaction. This structural stability was corroborated by sustained >90 % FDCA selectivity over five consecutive reaction cycles. This work established a dual-metal synergy strategy for multi-step oxidation pathways, offering insights into the design of robust catalysts for biomass-derived platform molecule upgrading.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"580 ","pages":"Article 115135"},"PeriodicalIF":3.9,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143847829","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0