Wenbin Qu, Bountheva Louangsouphom, Xiaoling Ye, Huimei Liu, Xin Wang
Integrating photocatalysis with adsorption represents an efficient approach to improving the removal performance of organic contaminants from aqueous environments. To address the issues of severe charge recombination and poor adsorption activity in TiO2 photocatalysts during the photocatalytic degradation of organic pollutants. In this study, we used macroporous resin as a carrier and prepared La/N-doped TiO2/macroporous resin composite materials (La/N/TiO2-MAR) via a hydrothermal-assisted sol–gel method. The results show that the composite material has a spherical morphology. N can be doped into the TiO2 crystal, while La3+ remains on the surface of TiO2 without entering the crystal lattice. La/N/TiO2-MAR demonstrates a higher specific surface area and enhanced light absorption capacity, which facilitates both adsorption and photocatalytic degradation. At the La3+ doping concentration of 0.05 M, La0.05/N/TiO2-MAR demonstrates optimal photocatalytic degradation performance, achieving an 85.36% removal rate of Rhodamine B after 240 min of visible-light exposure.
{"title":"Macroporous Resin-Based La-N Co-Doped TiO2 Composites for Efficient Removal of Environmental Pollutants in Water via Integrating Adsorption and Photocatalysis","authors":"Wenbin Qu, Bountheva Louangsouphom, Xiaoling Ye, Huimei Liu, Xin Wang","doi":"10.3390/catal15080759","DOIUrl":"https://doi.org/10.3390/catal15080759","url":null,"abstract":"Integrating photocatalysis with adsorption represents an efficient approach to improving the removal performance of organic contaminants from aqueous environments. To address the issues of severe charge recombination and poor adsorption activity in TiO2 photocatalysts during the photocatalytic degradation of organic pollutants. In this study, we used macroporous resin as a carrier and prepared La/N-doped TiO2/macroporous resin composite materials (La/N/TiO2-MAR) via a hydrothermal-assisted sol–gel method. The results show that the composite material has a spherical morphology. N can be doped into the TiO2 crystal, while La3+ remains on the surface of TiO2 without entering the crystal lattice. La/N/TiO2-MAR demonstrates a higher specific surface area and enhanced light absorption capacity, which facilitates both adsorption and photocatalytic degradation. At the La3+ doping concentration of 0.05 M, La0.05/N/TiO2-MAR demonstrates optimal photocatalytic degradation performance, achieving an 85.36% removal rate of Rhodamine B after 240 min of visible-light exposure.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"15 8","pages":"759-759"},"PeriodicalIF":0.0,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.mdpi.com/2073-4344/15/8/759/pdf?version=1754648746","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147332577","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yitong Zhao, Meng Liu, Ning Yao, Ying Zhang, Wu Zhi
In our previous work, we fabricated Ni single-atoms within Beta zeolite (Ni1@Beta-NO3−) using NiNO3·6H2O as a metal precursor without any chelating agents, which exhibited exceptional performance in the selective hydrogenation of furfural. Owing to the confinement effect, the as-encapsulated nickel species appears in the form of Ni0 and Niδ+, which implies its feasibility in metal catalysis and coordination catalysis. In the study reported herein, we further explored the hydrogen production and olefin oligomerization performance of Ni1@Beta-NO3−. It was found that Ni1@Beta-NO3− demonstrated a high H2 generation turnover frequency (TOF) and low activation energy (Ea) in a sodium borohydride (NaBH4) hydrolysis reaction, with values of 331 min−1 and 30.1 kJ/mol, respectively. In ethylene dimerization, it exhibited a high butylene selectivity of 99.4% and a TOF as high as 5804 h−1. In propylene oligomerization, Ni1@Beta-NO3− demonstrated high selectivity (75.21%) of long-chain olefins (≥C6+), overcoming the problem of cracking reactions that occur during oligomerization using H-Beta. Additionally, as a comparison, the influence of the metal precursor (NiCl2) on the performance of the encapsulated Ni catalyst was also examined. This research expands the application scenarios of non-noble metal single-atom catalysts and provides significant assistance and potential for the production of H2 from hydrogen storage materials and the production of valuable chemicals.
{"title":"The Catalytic Consequence of Isolated Ni Single-Atoms in BEA Zeolite for Hydrogen Production and Olefin Conversion","authors":"Yitong Zhao, Meng Liu, Ning Yao, Ying Zhang, Wu Zhi","doi":"10.3390/catal15080703","DOIUrl":"https://doi.org/10.3390/catal15080703","url":null,"abstract":"In our previous work, we fabricated Ni single-atoms within Beta zeolite (Ni1@Beta-NO3−) using NiNO3·6H2O as a metal precursor without any chelating agents, which exhibited exceptional performance in the selective hydrogenation of furfural. Owing to the confinement effect, the as-encapsulated nickel species appears in the form of Ni0 and Niδ+, which implies its feasibility in metal catalysis and coordination catalysis. In the study reported herein, we further explored the hydrogen production and olefin oligomerization performance of Ni1@Beta-NO3−. It was found that Ni1@Beta-NO3− demonstrated a high H2 generation turnover frequency (TOF) and low activation energy (Ea) in a sodium borohydride (NaBH4) hydrolysis reaction, with values of 331 min−1 and 30.1 kJ/mol, respectively. In ethylene dimerization, it exhibited a high butylene selectivity of 99.4% and a TOF as high as 5804 h−1. In propylene oligomerization, Ni1@Beta-NO3− demonstrated high selectivity (75.21%) of long-chain olefins (≥C6+), overcoming the problem of cracking reactions that occur during oligomerization using H-Beta. Additionally, as a comparison, the influence of the metal precursor (NiCl2) on the performance of the encapsulated Ni catalyst was also examined. This research expands the application scenarios of non-noble metal single-atom catalysts and provides significant assistance and potential for the production of H2 from hydrogen storage materials and the production of valuable chemicals.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"15 8","pages":"703-703"},"PeriodicalIF":0.0,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.mdpi.com/2073-4344/15/8/703/pdf?version=1753346832","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147333511","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
H. F. Xu, Hongwei Li, Xin An, Weiping Li, Rong Liu, Xinhong Zhao, Guixian Li
The methanol oxidation reaction (MOR) of direct methanol fuel cells (DMFCs) is limited by the slow kinetic process and high reaction energy barrier, significantly restricting the commercial application of DMFCs. Therefore, developing MOR catalysts with high activity and stability is very important. In this paper, oxygen-functionalised activated carbon (FAC) with controllable oxygen-containing functional groups was prepared by adjusting the volume ratio of H2SO3/HNO3 mixed acid, and Pd/AC and Pd/FAC catalysts were synthesised via the hydrazine hydrate reduction method. A series of characterisation techniques and electrochemical performance tests were used to study the catalyst. The results showed that when V(H2SO3):V(HNO3) = 2:3, more defects were generated on the surface of the AC, and more oxygen-containing functional groups represented by C=O and C–OH were attached to the surface of the support, which increased the anchor sites of Pd and improved the dispersion of Pd nanoparticles (Pd NPs) on the support. At the same time, the mass–specific activity of Pd/FAC for MOR was 2320 mA·mgPd, which is 1.5 times that of Pd/AC, and the stability was also improved to a certain extent. In situ infrared spectroscopy further confirmed that oxygen functionalisation treatment promoted the formation and transformation of *COOH intermediates, accelerated the transformation of COL into COB, reduced the poisoning of COads species adsorbed to the catalyst, optimised the reaction path and improved the catalytic kinetic performance.
{"title":"Effect of Oxygen-Containing Functional Groups on the Performance of Palladium/Carbon Catalysts for Electrocatalytic Oxidation of Methanol","authors":"H. F. Xu, Hongwei Li, Xin An, Weiping Li, Rong Liu, Xinhong Zhao, Guixian Li","doi":"10.3390/catal15080704","DOIUrl":"https://doi.org/10.3390/catal15080704","url":null,"abstract":"The methanol oxidation reaction (MOR) of direct methanol fuel cells (DMFCs) is limited by the slow kinetic process and high reaction energy barrier, significantly restricting the commercial application of DMFCs. Therefore, developing MOR catalysts with high activity and stability is very important. In this paper, oxygen-functionalised activated carbon (FAC) with controllable oxygen-containing functional groups was prepared by adjusting the volume ratio of H2SO3/HNO3 mixed acid, and Pd/AC and Pd/FAC catalysts were synthesised via the hydrazine hydrate reduction method. A series of characterisation techniques and electrochemical performance tests were used to study the catalyst. The results showed that when V(H2SO3):V(HNO3) = 2:3, more defects were generated on the surface of the AC, and more oxygen-containing functional groups represented by C=O and C–OH were attached to the surface of the support, which increased the anchor sites of Pd and improved the dispersion of Pd nanoparticles (Pd NPs) on the support. At the same time, the mass–specific activity of Pd/FAC for MOR was 2320 mA·mgPd, which is 1.5 times that of Pd/AC, and the stability was also improved to a certain extent. In situ infrared spectroscopy further confirmed that oxygen functionalisation treatment promoted the formation and transformation of *COOH intermediates, accelerated the transformation of COL into COB, reduced the poisoning of COads species adsorbed to the catalyst, optimised the reaction path and improved the catalytic kinetic performance.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"15 8","pages":"704-704"},"PeriodicalIF":0.0,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147333503","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The dry reforming of methane (DRM) and the combined steam–CO2 reforming of methane (CSCRM) are promising routes for syngas production while simultaneously utilizing two major greenhouse gases—CO2 and CH4. In this study, a series of Ni/MgO-Al2O3 catalysts with varying Mg/Al molar ratios (Ni/MgAl(x), x = 0.5–0.9), along with Ni/MgO and Ni/Al2O3, were synthesized, characterized, and evaluated in both the DRM and CSCRM. Ni/MgO and Ni/Al2O3 exhibited a lower activity due to fewer active sites and a poor CH4/CO2 activation balance. In contrast, Ni/MgAl(0.6), Ni/MgAl(0.7), and Ni/MgAl(0.8) showed an enhanced activity, attributed to more abundant active sites and a more balanced activation of CH4 and CO2. Ni/MgAl(0.7) delivered the best DRM performance, whereas Ni/MgAl(0.8) was optimal for the CSCRM, likely due to its greater number of strong basic sites promoting CO2 and H2O adsorption. At 750 °C and 0.1 MPa over 100 h, Ni/MgAl(0.7) maintained a stable DRM performance (77% CH4 and 86% CO2 conversion; H2/CO = 0.9) at 120 L/(gcat·h), while Ni/MgAl(0.8) achieved a stable CSCRM performance (80% CH4 and 62% CO2 conversion; H2/CO = 2.1) at 132 L/(gcat·h). This study provides valuable insights into designing efficient Ni/MgO-Al2O3 catalysts for targeted syngas production.
{"title":"Comparative Study on Ni/MgO-Al2O3 Catalysts for Dry and Combined Steam–CO2 Reforming of Methane","authors":"Tingting Zheng, Yuqi Zhou, Hongjie Cui, Zhiming Zhou","doi":"10.3390/catal15070659","DOIUrl":"https://doi.org/10.3390/catal15070659","url":null,"abstract":"The dry reforming of methane (DRM) and the combined steam–CO2 reforming of methane (CSCRM) are promising routes for syngas production while simultaneously utilizing two major greenhouse gases—CO2 and CH4. In this study, a series of Ni/MgO-Al2O3 catalysts with varying Mg/Al molar ratios (Ni/MgAl(x), x = 0.5–0.9), along with Ni/MgO and Ni/Al2O3, were synthesized, characterized, and evaluated in both the DRM and CSCRM. Ni/MgO and Ni/Al2O3 exhibited a lower activity due to fewer active sites and a poor CH4/CO2 activation balance. In contrast, Ni/MgAl(0.6), Ni/MgAl(0.7), and Ni/MgAl(0.8) showed an enhanced activity, attributed to more abundant active sites and a more balanced activation of CH4 and CO2. Ni/MgAl(0.7) delivered the best DRM performance, whereas Ni/MgAl(0.8) was optimal for the CSCRM, likely due to its greater number of strong basic sites promoting CO2 and H2O adsorption. At 750 °C and 0.1 MPa over 100 h, Ni/MgAl(0.7) maintained a stable DRM performance (77% CH4 and 86% CO2 conversion; H2/CO = 0.9) at 120 L/(gcat·h), while Ni/MgAl(0.8) achieved a stable CSCRM performance (80% CH4 and 62% CO2 conversion; H2/CO = 2.1) at 132 L/(gcat·h). This study provides valuable insights into designing efficient Ni/MgO-Al2O3 catalysts for targeted syngas production.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"15 7","pages":"659-659"},"PeriodicalIF":0.0,"publicationDate":"2025-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.mdpi.com/2073-4344/15/7/659/pdf?version=1751796062","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147331128","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Han Li, Mengting Zhang, Hao Li, Hai Ding, Jingjing Zhao, Yujia Zhang, Lang Wu, Chuanmei Jiao, Jie Feng, Zhikun Peng
Microwave-assisted ionothermal strategies offer an effective pathway for rapid zeolite crystallization under mild conditions, while conventional ionothermal approaches are still constrained by prolonged crystallization cycles that limit their industrial applicability. Herein, we report a microwave-activated, ionic liquid-mediated synthesis strategy that enables the precise modulation of crystallization kinetics and composite assembly. By introducing ZSM-5 seeds into the ionic liquid system, the nucleation and growth of AlPO4-5 were significantly accelerated, reducing crystallization time by up to 75% (optimal condition: 60 min). Among various imidazolium-based ionic liquids, [BMMIm]Br demonstrated an optimal balance of hydrophilic and hydrophobic interactions, yielding composite zeolites with high surface area (350 m2·g−1) and large pore volume (0.28 cm3·g−1). Comprehensive characterization (XRD, SEM-EDX, NH3-TPD) confirmed the formation of well-defined ZSM-5/AlPO4-5 core–shell structures and revealed tunable acid site distributions depending on the ionic liquid used. In methanol to olefins (MTO) reactions, the composite catalyst exhibited outstanding selectivity towards light olefins (C2=–C4=: 72.84%), markedly outperforming the individual ZSM-5 and AlPO4-5 components. The superior catalytic behavior is primarily attributed to the synergistic effect of hierarchical acid site tuning and the integrated core–shell architecture, which together optimize reaction selectivity. This strategy provides a promising route for the rational design of high-performance zeolites with significant industrial applicability.
{"title":"Rapid Fabrication of ZSM-5/AlPO4-5 Composites via Microwave-Ionothermal Strategy for Enhanced Methanol-to-Olefins Catalysis","authors":"Han Li, Mengting Zhang, Hao Li, Hai Ding, Jingjing Zhao, Yujia Zhang, Lang Wu, Chuanmei Jiao, Jie Feng, Zhikun Peng","doi":"10.3390/catal15060605","DOIUrl":"https://doi.org/10.3390/catal15060605","url":null,"abstract":"Microwave-assisted ionothermal strategies offer an effective pathway for rapid zeolite crystallization under mild conditions, while conventional ionothermal approaches are still constrained by prolonged crystallization cycles that limit their industrial applicability. Herein, we report a microwave-activated, ionic liquid-mediated synthesis strategy that enables the precise modulation of crystallization kinetics and composite assembly. By introducing ZSM-5 seeds into the ionic liquid system, the nucleation and growth of AlPO4-5 were significantly accelerated, reducing crystallization time by up to 75% (optimal condition: 60 min). Among various imidazolium-based ionic liquids, [BMMIm]Br demonstrated an optimal balance of hydrophilic and hydrophobic interactions, yielding composite zeolites with high surface area (350 m2·g−1) and large pore volume (0.28 cm3·g−1). Comprehensive characterization (XRD, SEM-EDX, NH3-TPD) confirmed the formation of well-defined ZSM-5/AlPO4-5 core–shell structures and revealed tunable acid site distributions depending on the ionic liquid used. In methanol to olefins (MTO) reactions, the composite catalyst exhibited outstanding selectivity towards light olefins (C2=–C4=: 72.84%), markedly outperforming the individual ZSM-5 and AlPO4-5 components. The superior catalytic behavior is primarily attributed to the synergistic effect of hierarchical acid site tuning and the integrated core–shell architecture, which together optimize reaction selectivity. This strategy provides a promising route for the rational design of high-performance zeolites with significant industrial applicability.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"15 6","pages":"605-605"},"PeriodicalIF":0.0,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147332860","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The efficient removal of emulsified oil and trace organic pollutants via forward osmosis (FO) technology remains challenging due to limited water flux and membrane fouling. In this study, a series of metal oxide-modified PES-based composite FO membranes were fabricated and systematically evaluated to compare the effects of ZnO, Al2O3, and CuO nanoparticles on membrane structure and separation performance. The results demonstrated that the membrane modified with 0.04 g of ZnO nanoparticles achieved optimal synergy in terms of hydrophilicity, surface charge, and pore structure. The pure water flux increased from 5.48 L·m−2·h−1 for the pristine membrane to 18.5 L·m−2·h−1 for the ZnO-modified membrane, exhibiting a 237.5% increase in pure water flux compared to the pristine PES membrane, an oil rejection rate exceeding 97%, and over 95% rejection of typical negatively charged trace organic pollutants such as ibuprofen and tetracycline. Moreover, the ZnO-modified membrane showed excellent antifouling performance and structural stability in various organic solvent systems. This study not only optimized the interfacial chemistry and microstructure of the FO membrane but also enhanced pollutant repellence and the self-cleaning capability through increased hydrophilicity and surface negative charge density. These findings highlight the significant potential of ZnO modification for enhancing the overall performance of FO membranes and provide an effective strategy for developing high-performance, broadly applicable FO membranes for complex water purification.
由于水通量有限和膜污染，通过正向渗透（FO）技术高效去除乳化油和微量有机污染物仍然具有挑战性。在本研究中，制备了一系列金属氧化物修饰的聚砜基复合FO膜，并对其进行了系统评价，比较了ZnO、Al2O3和CuO纳米颗粒对膜结构和分离性能的影响。结果表明，0.04 g ZnO纳米粒子修饰的膜在亲水性、表面电荷和孔结构方面均达到最佳协同效果。纯水通量由原始膜的5.48 L·m−2·h−1提高到18.5 L·m−2·h−1，与原始膜相比，纯水通量提高了237.5%，滤油率超过97%，对典型的带负电荷的微量有机污染物如布洛芬和四环素的去除率超过95%。此外，zno改性膜在各种有机溶剂体系中均表现出优异的防污性能和结构稳定性。本研究不仅优化了FO膜的界面化学和微观结构，而且通过提高亲水性和表面负电荷密度，增强了FO膜的拒污性和自清洁能力。这些发现突出了ZnO改性在提高FO膜整体性能方面的巨大潜力，并为开发高性能、广泛应用于复杂水净化的FO膜提供了有效的策略。
{"title":"Metal Oxide-Modified PES Membranes for Efficient Separation of Oil-in-Water Emulsions and Trace Organic Compounds","authors":"Jinze Li, Wensheng Yang, Yang Xu, Chengfeng Sun, Yingying Zhu, Geng Chen","doi":"10.3390/catal15060604","DOIUrl":"https://doi.org/10.3390/catal15060604","url":null,"abstract":"The efficient removal of emulsified oil and trace organic pollutants via forward osmosis (FO) technology remains challenging due to limited water flux and membrane fouling. In this study, a series of metal oxide-modified PES-based composite FO membranes were fabricated and systematically evaluated to compare the effects of ZnO, Al2O3, and CuO nanoparticles on membrane structure and separation performance. The results demonstrated that the membrane modified with 0.04 g of ZnO nanoparticles achieved optimal synergy in terms of hydrophilicity, surface charge, and pore structure. The pure water flux increased from 5.48 L·m−2·h−1 for the pristine membrane to 18.5 L·m−2·h−1 for the ZnO-modified membrane, exhibiting a 237.5% increase in pure water flux compared to the pristine PES membrane, an oil rejection rate exceeding 97%, and over 95% rejection of typical negatively charged trace organic pollutants such as ibuprofen and tetracycline. Moreover, the ZnO-modified membrane showed excellent antifouling performance and structural stability in various organic solvent systems. This study not only optimized the interfacial chemistry and microstructure of the FO membrane but also enhanced pollutant repellence and the self-cleaning capability through increased hydrophilicity and surface negative charge density. These findings highlight the significant potential of ZnO modification for enhancing the overall performance of FO membranes and provide an effective strategy for developing high-performance, broadly applicable FO membranes for complex water purification.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"15 6","pages":"604-604"},"PeriodicalIF":0.0,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.mdpi.com/2073-4344/15/6/604/pdf?version=1750342841","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147331332","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Owing to global energy demands and climate change resulting from fossil fuel use, technologies capable of converting greenhouse gases into renewable energy resources are needed. One such technology is photocatalytic CO2 reduction, which utilises solar energy to transform CO2 into value-added hydrocarbons. However, the application of photocatalytic CO2 reduction is limited by the inefficiency of existing photocatalysts. In this study, we developed a nitrogen-deficient g-C3N4-confined PtCu dual-atom catalyst (PtCu/VN-C3N4) for photocatalytic CO2 reduction. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure spectroscopy confirmed the atomic-level anchoring of PtCu pairs onto the nitrogen-vacancy-rich g-C3N4 nanosheets. The optimised PtCu/VN-C3N4 exhibited superior photocatalytic performance, with CO and CH4 evolution rates of 13.3 µmol/g/h and 2.5 µmol/g/h, respectively, under visible-light irradiation. Mechanistic investigations revealed that CO2 molecules were preferentially adsorbed onto the PtCu dual sites, initiating a stepwise reduction pathway. In situ diffuse reflectance infrared Fourier-transform spectroscopy identified the formation of a key intermediate (HCOO*), whereas interfacial wettability studies demonstrated efficient H2O adsorption on PtCu sites, providing essential proton sources for CO2 protonation. Photoelectrochemical characterisation further confirmed the enhanced charge-transfer kinetics in PtCu/VN-C3N4, which were attributed to the synergistic interplay between the nitrogen vacancies and dual-atom sites. Notably, the dual-active-site architecture minimised the competitive adsorption between CO2 and H2O molecules, thereby optimising the surface reaction pathways. This study establishes a rational strategy for designing atomically precise dual-atom catalysts through defect engineering, achieving concurrent improvements in activity, selectivity, and charge carrier utilisation for solar-driven CO2 conversion.
{"title":"Nitrogen-Defect-Driven PtCu Dual-Atom Catalyst for Photocatalytic CO2 Reduction","authors":"He Xin, Ting Liu, Hao Wang, Yongming Luo","doi":"10.3390/catal15060558","DOIUrl":"https://doi.org/10.3390/catal15060558","url":null,"abstract":"Owing to global energy demands and climate change resulting from fossil fuel use, technologies capable of converting greenhouse gases into renewable energy resources are needed. One such technology is photocatalytic CO2 reduction, which utilises solar energy to transform CO2 into value-added hydrocarbons. However, the application of photocatalytic CO2 reduction is limited by the inefficiency of existing photocatalysts. In this study, we developed a nitrogen-deficient g-C3N4-confined PtCu dual-atom catalyst (PtCu/VN-C3N4) for photocatalytic CO2 reduction. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure spectroscopy confirmed the atomic-level anchoring of PtCu pairs onto the nitrogen-vacancy-rich g-C3N4 nanosheets. The optimised PtCu/VN-C3N4 exhibited superior photocatalytic performance, with CO and CH4 evolution rates of 13.3 µmol/g/h and 2.5 µmol/g/h, respectively, under visible-light irradiation. Mechanistic investigations revealed that CO2 molecules were preferentially adsorbed onto the PtCu dual sites, initiating a stepwise reduction pathway. In situ diffuse reflectance infrared Fourier-transform spectroscopy identified the formation of a key intermediate (HCOO*), whereas interfacial wettability studies demonstrated efficient H2O adsorption on PtCu sites, providing essential proton sources for CO2 protonation. Photoelectrochemical characterisation further confirmed the enhanced charge-transfer kinetics in PtCu/VN-C3N4, which were attributed to the synergistic interplay between the nitrogen vacancies and dual-atom sites. Notably, the dual-active-site architecture minimised the competitive adsorption between CO2 and H2O molecules, thereby optimising the surface reaction pathways. This study establishes a rational strategy for designing atomically precise dual-atom catalysts through defect engineering, achieving concurrent improvements in activity, selectivity, and charge carrier utilisation for solar-driven CO2 conversion.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"15 6","pages":"558-558"},"PeriodicalIF":0.0,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.mdpi.com/2073-4344/15/6/558/pdf?version=1749029250","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147333638","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Despite significant advancements in designing tandem catalysts for CO2 hydrogenation to aromatics, the role of zeolite acid property in regulating the selectivity of light aromatics (benzene, toluene, and xylene, abbreviated as BTX) remains unclear. Herein, we report H-ZSM-5 zeolite (denoted as HZ-X, where X represents the Si/Al ratio) integrated with a Na-promoted FeCo-based catalyst (NaFeCo) for CO2 hydrogenation into aromatics via a modified Fischer–Tropsch synthesis pathway. This study systematically modulates the Si/Al ratio of acidic zeolite and examines its critical role in influencing the light aromatics selectivity. The optimized NaFeCo/HZ-50 catalyst achieves a CO2 conversion of 43% with an aromatics selectivity of 41%, including a BTX fraction of 57% in total aromatics. Multiple characterization techniques (NH3-TPD, Py/DTBPy-IR, 27Al NMR, etc.) clarify that acidic zeolite HZ-50 exhibits appropriate acid density and lower external surface acid sites, which synergistically boost the efficient aromatics and BTX synthesis while suppressing the undesirable alkylation and isomerization reactions on the external acid sites. This work develops a highly efficient multifunctional catalyst for CO2 hydrogenation to light aromatics, especially offering guidance for the rational design of acidic zeolite with unique shape-selective functions.
{"title":"Modified Fischer–Tropsch Pathway for CO2 Hydrogenation to Aromatics: Impact of Si/Al Ratio of H-ZSM-5 Zeolite on Light Aromatics Selectivity","authors":"Shaocong Wang, Yu Sun, Shiyuan Lin, Zhi Bian, Yuanyuan Han, Xinze Bi, Zhaorui Zhang, Xiaojie Liu, Dandan Liu, Yang Wang, Mingbo Wu","doi":"10.3390/catal15060557","DOIUrl":"https://doi.org/10.3390/catal15060557","url":null,"abstract":"Despite significant advancements in designing tandem catalysts for CO2 hydrogenation to aromatics, the role of zeolite acid property in regulating the selectivity of light aromatics (benzene, toluene, and xylene, abbreviated as BTX) remains unclear. Herein, we report H-ZSM-5 zeolite (denoted as HZ-X, where X represents the Si/Al ratio) integrated with a Na-promoted FeCo-based catalyst (NaFeCo) for CO2 hydrogenation into aromatics via a modified Fischer–Tropsch synthesis pathway. This study systematically modulates the Si/Al ratio of acidic zeolite and examines its critical role in influencing the light aromatics selectivity. The optimized NaFeCo/HZ-50 catalyst achieves a CO2 conversion of 43% with an aromatics selectivity of 41%, including a BTX fraction of 57% in total aromatics. Multiple characterization techniques (NH3-TPD, Py/DTBPy-IR, 27Al NMR, etc.) clarify that acidic zeolite HZ-50 exhibits appropriate acid density and lower external surface acid sites, which synergistically boost the efficient aromatics and BTX synthesis while suppressing the undesirable alkylation and isomerization reactions on the external acid sites. This work develops a highly efficient multifunctional catalyst for CO2 hydrogenation to light aromatics, especially offering guidance for the rational design of acidic zeolite with unique shape-selective functions.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"15 6","pages":"557-557"},"PeriodicalIF":0.0,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.mdpi.com/2073-4344/15/6/557/pdf?version=1749025218","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147333645","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Phenylalanine butyramide (FBA) is a novel butyric acid derivative with favorable sensory properties, which has broad prospects in medicine and feed processing. However, there is currently limited research on the enzymatic synthesis of FBA. As is well known, lipase plays a crucial role in amide bond synthesis, but it typically requires completely anhydrous conditions. The lipase from Sphingomonas sp. HXN-200 (SpL) is the only intracellular lipase identified to date, capable of catalyzing the ammonolysis of esters or acids in an aqueous phase. In this study, we developed a method for the synthesis of FBA catalyzed by SpL in a biphasic reaction system of water and n-hexane. SpL was successfully expressed in E. coli BL21, and the optimal induction conditions were 0.4 mM IPTG and 18 h. It was ascertained that the n-hexane system containing 2% water was conducive to the reaction. Under optimized reaction conditions, 0.89 mg/mL of FBA was obtained within 15 h at 30 °C. Additionally, we found that SpL also has the ability to hydrolyze amides in the reaction of SpL catalyzing the formation of amides, so we further analyzed its catalytic mechanism.
{"title":"Intracellular Lipases for Enzymatic Synthesis of Phenylalanine Butyramide in a Biphasic Reaction System","authors":"Xinyu Fan, Pengcheng Chen, Dan Wu, Pu Zheng","doi":"10.3390/catal15060514","DOIUrl":"https://doi.org/10.3390/catal15060514","url":null,"abstract":"Phenylalanine butyramide (FBA) is a novel butyric acid derivative with favorable sensory properties, which has broad prospects in medicine and feed processing. However, there is currently limited research on the enzymatic synthesis of FBA. As is well known, lipase plays a crucial role in amide bond synthesis, but it typically requires completely anhydrous conditions. The lipase from Sphingomonas sp. HXN-200 (SpL) is the only intracellular lipase identified to date, capable of catalyzing the ammonolysis of esters or acids in an aqueous phase. In this study, we developed a method for the synthesis of FBA catalyzed by SpL in a biphasic reaction system of water and n-hexane. SpL was successfully expressed in E. coli BL21, and the optimal induction conditions were 0.4 mM IPTG and 18 h. It was ascertained that the n-hexane system containing 2% water was conducive to the reaction. Under optimized reaction conditions, 0.89 mg/mL of FBA was obtained within 15 h at 30 °C. Additionally, we found that SpL also has the ability to hydrolyze amides in the reaction of SpL catalyzing the formation of amides, so we further analyzed its catalytic mechanism.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"15 6","pages":"514-514"},"PeriodicalIF":0.0,"publicationDate":"2025-05-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147333453","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Bio-oil is a potential source for the production of alternative fuels and chemicals. In this work, Ni-V bimetallic zeolite catalysts were synthesized and evaluated in in situ catalytic hydrodeoxygenation (HDO) of pyrolysis volatiles of pine nut shell for upgraded bio-oil products. The pH and lower heating value (LHV) of the upgraded bio-oil products were improved by in situ catalytic HDO, while the moisture content and density of the oil decreased. The O/C ratio of the upgraded bio-oil products decreased significantly, and the oxygenated compounds in the pyrolysis volatiles were converted efficiently via deoxygenation over Ni-V zeolite catalysts. The highest HDO activity was obtained with NiV/MesoY, where the obtained bio-oil had the lowest O/C atomic ratio (0.27), a higher LHV (27.03 MJ/kg) and the highest selectivity (19.6%) towards target arenes. Owing to the more appropriate pore size distribution and better dispersion of metal active sites, NiV/MesoY enhanced the transformation of reacting intermediates, obtaining the dominant products of phenols and arenes. A higher HDO temperature improved the catalytic activity of pyrolysis volatiles to form more deoxygenated arenes. Higher Ni loading could generate more metal active sites, thus promoting the catalyst’s HDO activity for pyrolysis volatiles. This study contributes to the development of cost-efficient and eco-friendly HDO catalysts, which are required for producing high-quality biofuel products.
{"title":"Catalytic Hydrodeoxygenation of Pyrolysis Volatiles from Pine Nut Shell over Ni-V Bimetallic Catalysts Supported on Zeolites","authors":"Yujian Wu, Xiwei Xu, Xudong Fan, Yan Sun, Ren Tu, Enchen Jiang, Qing Xu, Chunbao Xu","doi":"10.3390/catal15050498","DOIUrl":"https://doi.org/10.3390/catal15050498","url":null,"abstract":"Bio-oil is a potential source for the production of alternative fuels and chemicals. In this work, Ni-V bimetallic zeolite catalysts were synthesized and evaluated in in situ catalytic hydrodeoxygenation (HDO) of pyrolysis volatiles of pine nut shell for upgraded bio-oil products. The pH and lower heating value (LHV) of the upgraded bio-oil products were improved by in situ catalytic HDO, while the moisture content and density of the oil decreased. The O/C ratio of the upgraded bio-oil products decreased significantly, and the oxygenated compounds in the pyrolysis volatiles were converted efficiently via deoxygenation over Ni-V zeolite catalysts. The highest HDO activity was obtained with NiV/MesoY, where the obtained bio-oil had the lowest O/C atomic ratio (0.27), a higher LHV (27.03 MJ/kg) and the highest selectivity (19.6%) towards target arenes. Owing to the more appropriate pore size distribution and better dispersion of metal active sites, NiV/MesoY enhanced the transformation of reacting intermediates, obtaining the dominant products of phenols and arenes. A higher HDO temperature improved the catalytic activity of pyrolysis volatiles to form more deoxygenated arenes. Higher Ni loading could generate more metal active sites, thus promoting the catalyst’s HDO activity for pyrolysis volatiles. This study contributes to the development of cost-efficient and eco-friendly HDO catalysts, which are required for producing high-quality biofuel products.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":"15 5","pages":"498-498"},"PeriodicalIF":0.0,"publicationDate":"2025-05-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.mdpi.com/2073-4344/15/5/498/pdf?version=1747753143","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147332990","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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