Pub Date : 2025-03-06DOI: 10.1016/j.jcat.2025.116058
Jiashi Chen , Xingyu Chen , Xiyue Cao , Huijuan Ma , Xuanfeng Jiang , Zhengguang Sun , Yuan Zhan
Photocatalysis is an environmentally friendly strategy for synthesis of high-value chemicals. However, covalent organic frameworks (COFs), as organic semiconductors, typically exhibit limited electrical conductivity, which significantly affects the photocatalytic efficiency of COF. In this work, a simple hydrothermal treatment method was presented to enhance the conductivity of aza-COF prepared by acid-catalyzed imine condensation of BTA⋅4HCl and HKH⋅8H2O. The crystallinity and carbonization degree of the aza-COF were explored by adjusting the hydrothermal temperatures from 80 to 160 °C. Remarkably, the COF-3 prepared by 120 °C hydrothermal temperature displays the highest photocatalytic conversion rate of benzylamine of 97 % with the high selectivity of 99 % in 4 h, outperforming the pristine aza-COF by 40 %. From various test results analysis, COF-3 exhibits the strongest transient photocurrent response, smallest electrochemical impedance, narrowest bandgap energy, attributed to its enhanced crystallinity, which improves conductivity. Furthermore, the photocatalysis mechanism was elucidated through quenching experiments, which determined the reactive oxygen species.
{"title":"Hydrothermal assisted enhancing crystallinity of COF towards effective photocatalytic oxidation of benzylamines","authors":"Jiashi Chen , Xingyu Chen , Xiyue Cao , Huijuan Ma , Xuanfeng Jiang , Zhengguang Sun , Yuan Zhan","doi":"10.1016/j.jcat.2025.116058","DOIUrl":"10.1016/j.jcat.2025.116058","url":null,"abstract":"<div><div>Photocatalysis is an environmentally friendly strategy for synthesis of high-value chemicals. However, covalent organic frameworks (COFs), as organic semiconductors, typically exhibit limited electrical conductivity, which significantly affects the photocatalytic efficiency of COF. In this work, a simple hydrothermal treatment method was presented to enhance the conductivity of aza-COF prepared by acid-catalyzed imine condensation of BTA⋅4HCl and HKH⋅8H<sub>2</sub>O. The crystallinity and carbonization degree of the aza-COF were explored by adjusting the hydrothermal temperatures from 80 to 160 °C. Remarkably, the COF-3 prepared by 120 °C hydrothermal temperature displays the highest photocatalytic conversion rate of benzylamine of 97 % with the high selectivity of 99 % in 4 h, outperforming the pristine aza-COF by 40 %. From various test results analysis, COF-3 exhibits the strongest transient photocurrent response, smallest electrochemical impedance, narrowest bandgap energy, attributed to its enhanced crystallinity, which improves conductivity. Furthermore, the photocatalysis mechanism was elucidated through quenching experiments, which determined the reactive oxygen species.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"446 ","pages":"Article 116058"},"PeriodicalIF":6.5,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143569948","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-06DOI: 10.1016/j.jcat.2025.116059
Aojie Sun , Yu Ying , Meng Wang , Lin Zhu , Yidi Wang , Quan Zhang , Lanpeng Li , Changhai Cao , Haoxiang Xu , Daojian Cheng
To address the issue of the accumulation of water around Brønsted acid sites during the fructose dehydration towards 5-hydroxymethylfurfural (HMF), in this work, hydrophobic SAPO-34 is prepared by post-treatment silanization by grafting alkyl hydrophobic groups on its surface. The SAPO-34 catalyst modified with dodecyl trimethoxysilane exhibits a significantly enhanced yield of 5-hydroxymethylfurfural (HMF), reaching 95.05 %. It is determined that long-chain hydrophobic groups facilitate the forward reaction of fructose dehydration by creating a microenvironment favorable for water removal and fructose enrichment. Furthermore, it releases Brønsted acid sites from water molecules, and enhance fructose’s accessibility to Brønsted acid sites. Thus, the activity, selectivity and durability of SAPO-34 can be promoted simultaneously, due to the selective removal water rather than fructose. This work put insight into the role of alkyl chain length of hydrophobic groups in promoting fructose dehydration towards HMF, which may be guideline for other dehydration reactions restricted by water.
{"title":"Efficient conversion of fructose to 5-hydroxymethylfurfural by hydrophobic modified SAPO-34 molecular sieve","authors":"Aojie Sun , Yu Ying , Meng Wang , Lin Zhu , Yidi Wang , Quan Zhang , Lanpeng Li , Changhai Cao , Haoxiang Xu , Daojian Cheng","doi":"10.1016/j.jcat.2025.116059","DOIUrl":"10.1016/j.jcat.2025.116059","url":null,"abstract":"<div><div>To address the issue of the accumulation of water around Brønsted acid sites during the fructose dehydration towards 5-hydroxymethylfurfural (HMF), in this work, hydrophobic SAPO-34 is prepared by post-treatment silanization by grafting alkyl hydrophobic groups on its surface. The SAPO-34 catalyst modified with dodecyl trimethoxysilane exhibits a significantly enhanced yield of 5-hydroxymethylfurfural (HMF), reaching 95.05 %. It is determined that long-chain hydrophobic groups facilitate the forward reaction of fructose dehydration by creating a microenvironment favorable for water removal and fructose enrichment. Furthermore, it releases Brønsted acid sites from water molecules, and enhance fructose’s accessibility to Brønsted acid sites. Thus, the activity, selectivity and durability of SAPO-34 can be promoted simultaneously, due to the selective removal water rather than fructose. This work put insight into the role of alkyl chain length of hydrophobic groups in promoting fructose dehydration towards HMF, which may be guideline for other dehydration reactions restricted by water.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"446 ","pages":"Article 116059"},"PeriodicalIF":6.5,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143569950","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-06DOI: 10.1016/j.jcat.2025.116061
Peixin Yang , Qianyang Chang , Qi Zhang , Jian Yu , Xing Ji , Ying Zhang , Wenjing Yang , Peng Xiao , Yunhuai Zhang
Enhancing the selective oxidation of glycerol into 1,3-dihydroxyacetone (DHA) on a photoanode is attractive but challenging due to the complex reaction pathway. At present, the 20 % selectivity of DHA products on a BiVO4 photoanode in neutral condition as well as its photocorrosion prove to be below expectations. In this work, we decorated binary co-catalysts MnOx/FeOOH on BiVO4 (denoted BVO/Mn/Fe) for the selective photoelectrocatalytic glycerol to DHA. The BVO/Mn/Fe photoanode exhibited a DHA selectivity of 52 % at 1.2 VRHE with an evolution rate of 193.3 mmol m-2h−1 in pH = 7.0, and maintained 97.2 % of the initial photocurrent after 12 h stability test. The role of MnOx and FeOOH in the selective oxidation of glycerol was investigated through comprehensive spectroscopic and computational methods. Fourier transform infrared spectroscopy showed that the middle hydroxyl group preferentially adsorbs onto MnOx surfaces, density function theory calculations verified the optimized rate-determining step and decreased energy barrier by MnOx. Meanwhile, FeOOH significantly increased the active surface states on BiVO4 and produced more hydroxyl radicals. The synergistic effect of MnOx and FeOOH promoted the middle hydroxyl oxidation of glycerol and conversion efficiency to DHA on BiVO4 under neutral condition.
{"title":"Boost photoelectrocatalytic selectivity of glycerol to dihydroxyacetone on BiVO4 via accelerating middle hydroxyl oxidation by co-catalysts","authors":"Peixin Yang , Qianyang Chang , Qi Zhang , Jian Yu , Xing Ji , Ying Zhang , Wenjing Yang , Peng Xiao , Yunhuai Zhang","doi":"10.1016/j.jcat.2025.116061","DOIUrl":"10.1016/j.jcat.2025.116061","url":null,"abstract":"<div><div>Enhancing the selective oxidation of glycerol into 1,3-dihydroxyacetone (DHA) on a photoanode is attractive but challenging due to the complex reaction pathway. At present, the 20 % selectivity of DHA products on a BiVO<sub>4</sub> photoanode in neutral condition as well as its photocorrosion prove to be below expectations. In this work, we decorated binary co-catalysts MnO<sub>x</sub>/FeOOH on BiVO<sub>4</sub> (denoted BVO/Mn/Fe) for the selective photoelectrocatalytic glycerol to DHA. The BVO/Mn/Fe photoanode exhibited a DHA selectivity of 52 % at 1.2 V<sub>RHE</sub> with an evolution rate of 193.3 mmol m<sup>-2</sup>h<sup>−1</sup> in pH = 7.0, and maintained 97.2 % of the initial photocurrent after 12 h stability test. The role of MnO<sub>x</sub> and FeOOH in the selective oxidation of glycerol was investigated through comprehensive spectroscopic and computational methods. Fourier transform infrared spectroscopy showed that the middle hydroxyl group preferentially adsorbs onto MnO<sub>x</sub> surfaces, density function theory calculations verified the optimized rate-determining step and decreased energy barrier by MnO<sub>x</sub>. Meanwhile, FeOOH significantly increased the active surface states on BiVO<sub>4</sub> and produced more hydroxyl radicals. The synergistic effect of MnO<sub>x</sub> and FeOOH promoted the middle hydroxyl oxidation of glycerol and conversion efficiency to DHA on BiVO<sub>4</sub> under neutral condition.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"446 ","pages":"Article 116061"},"PeriodicalIF":6.5,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143569949","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Plastic pollution has become the second most significant environmental issue globally, following climate change. Traditional plastic recycling methods, such as mechanical and chemical recycling, suffer from low efficiency and significant ecological impacts. This study introduces a novel approach to the hydrogenolysis of polyesters and polycarbonates using a phosphine-free manganese-based pincer catalyst, achieving the efficient conversion of various plastics into valuable chemicals under mild conditions at lower temperatures and pressures. Experimental results demonstrate excellent catalytic activity and selectivity for transforming PET, PBT, PCL, PLA, and PC. Furthermore, the method has been successfully applied to the recycling of various commercial and post-consumer polyester and polycarbonate plastics, showcasing its potential for practical applications. This study not only provides a new perspective on plastic waste management but also offers important technical support for developing a circular economy.
{"title":"Innovative upcycling of polyesters and polycarbonates via manganese-catalyzed hydrogenolysis","authors":"Guoren Zhou , Chongyan Ren , Xiaoshi Zhang , Bocheng Xu , Maofu Pang , Xiaoxiao Chu","doi":"10.1016/j.jcat.2025.116060","DOIUrl":"10.1016/j.jcat.2025.116060","url":null,"abstract":"<div><div>Plastic pollution has become the second most significant environmental issue globally, following climate change. Traditional plastic recycling methods, such as mechanical and chemical recycling, suffer from low efficiency and significant ecological impacts. This study introduces a novel approach to the hydrogenolysis of polyesters and polycarbonates using a phosphine-free manganese-based pincer catalyst, achieving the efficient conversion of various plastics into valuable chemicals under mild conditions at lower temperatures and pressures. Experimental results demonstrate excellent catalytic activity and selectivity for transforming PET, PBT, PCL, PLA, and PC. Furthermore, the method has been successfully applied to the recycling of various commercial and post-consumer polyester and polycarbonate plastics, showcasing its potential for practical applications. This study not only provides a new perspective on plastic waste management but also offers important technical support for developing a circular economy.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"446 ","pages":"Article 116060"},"PeriodicalIF":6.5,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143569951","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-05DOI: 10.1016/j.jcat.2025.116056
Ting-Sheng Chen , Di Liu , Yun-Jie Li , Xing-Bao Wang , Chang-Hai Liang , Zhen-Yi Du , Wen-Ying Li
Controlling the oxygen-free product selectivity in catalytic hydrodeoxygenation is essential for producing high quality fuels from coal- and biomass-derived crude liquids. A series of boron-doped Ni/SiO2 catalysts were prepared for the efficient hydrodeoxygenation of dibenzofuran as a model compound. Boron doping significantly promoted the transformation of 2-cyclohexylcyclohexanol, which was accumulated as the main oxygen-containing intermediate compound on the pristine Ni/SiO2 catalyst, to the target products bicyclohexane and its isomer cyclopentylmethylcyclohexane. Characterization results show that boron doping increases Ni dispersion, modifies the electronic properties of Ni sites and in situ generates Brønsted acid sites by H2 spillover to boron oxides. The reduced Ni particle size improves the rates of dibenzofuran hydrogenation and 2-cyclohexylcyclohexanol dehydration. Electron-deficient Ni and boron oxides as the Lewis acid sites enhance the adsorption of 2-cyclohexylcyclohexanol. Furthermore, the in situ generated Brønsted acid sites favor the dehydration of 2-cyclohexylcyclohexanol, which gives the Ni-5B/SiO2 catalyst a better deoxygenation activity than the mechanical mixture of equal amounts of 5B/SiO2 and Ni/SiO2, as well as the one with a smaller Ni particle size of 3.8 nm.
{"title":"Promotional role of boron on Ni/SiO2 catalysts for dibenzofuran hydrodeoxygenation","authors":"Ting-Sheng Chen , Di Liu , Yun-Jie Li , Xing-Bao Wang , Chang-Hai Liang , Zhen-Yi Du , Wen-Ying Li","doi":"10.1016/j.jcat.2025.116056","DOIUrl":"10.1016/j.jcat.2025.116056","url":null,"abstract":"<div><div>Controlling the oxygen-free product selectivity in catalytic hydrodeoxygenation is essential for producing high quality fuels from coal- and biomass-derived crude liquids. A series of boron-doped Ni/SiO<sub>2</sub> catalysts were prepared for the efficient hydrodeoxygenation of dibenzofuran as a model compound. Boron doping significantly promoted the transformation of 2-cyclohexylcyclohexanol, which was accumulated as the main oxygen-containing intermediate compound on the pristine Ni/SiO<sub>2</sub> catalyst, to the target products bicyclohexane and its isomer cyclopentylmethylcyclohexane. Characterization results show that boron doping increases Ni dispersion, modifies the electronic properties of Ni sites and <em>in situ</em> generates Brønsted acid sites by H<sub>2</sub> spillover to boron oxides. The reduced Ni particle size improves the rates of dibenzofuran hydrogenation and 2-cyclohexylcyclohexanol dehydration. Electron-deficient Ni and boron oxides as the Lewis acid sites enhance the adsorption of 2-cyclohexylcyclohexanol. Furthermore, the <em>in situ</em> generated Brønsted acid sites favor the dehydration of 2-cyclohexylcyclohexanol, which gives the Ni-5B/SiO<sub>2</sub> catalyst a better deoxygenation activity than the mechanical mixture of equal amounts of 5B/SiO<sub>2</sub> and Ni/SiO<sub>2</sub>, as well as the one with a smaller Ni particle size of 3.8 nm.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"446 ","pages":"Article 116056"},"PeriodicalIF":6.5,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143560922","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Herein, we report the efficient synthesis of E-enamines with 100% regioselectivity by the hydroamination of various terminal alkynes with secondary amines (piperidine and piperazine) mediated by easily accessible tungsten(0) complex, at smooth conditions. We have successfully broadened the hydroamination protocol to obtain various new E-divinylpiperazines with excellent regio- and stereoselectivities. The crystal structure of two of them was determined, which allowed receiving information, among others, on the conformation of the C–C double bond. Furthermore, the reaction allows facile access to enamines containing the isoindoline-1,3-dione fragment with high regioselectivity. Selected divinylpiperazines have also been investigated by photoluminescence excitation and emission examination. On the basis of the experimental results, the pathway of the catalytic hydroamination of alkyne with piperazine has been proposed.
{"title":"Hydroamination of terminal alkynes mediated by W(0) complex: A convenient tool for new enamines synthesis","authors":"Izabela Czeluśniak , Paulina Pąchalska , Joanna Trojan-Piegza , Mariusz Majchrzak , Miłosz Siczek , Teresa Szymańska-Buzar","doi":"10.1016/j.jcat.2025.116057","DOIUrl":"10.1016/j.jcat.2025.116057","url":null,"abstract":"<div><div>Herein, we report the efficient synthesis of <em>E</em>-enamines with 100% regioselectivity by the hydroamination of various terminal alkynes with secondary amines (piperidine and piperazine) mediated by easily accessible tungsten(0) complex, at smooth conditions. We have successfully broadened the hydroamination protocol to obtain various new <em>E</em>-divinylpiperazines with excellent regio- and stereoselectivities. The crystal structure of two of them was determined, which allowed receiving information, among others, on the conformation of the C–C double bond. Furthermore, the reaction allows facile access to enamines containing the isoindoline-1,3-dione fragment with high regioselectivity. Selected divinylpiperazines have also been investigated by photoluminescence excitation and emission examination. On the basis of the experimental results, the pathway of the catalytic hydroamination of alkyne with piperazine has been proposed.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"446 ","pages":"Article 116057"},"PeriodicalIF":6.5,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561346","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-04DOI: 10.1016/j.jcat.2025.116051
Xiaolan Li , Jie Liu , Ruixin Song , Xuzhong Luo , Haiqing Luo
Rhodium(III)-catalyzed β-C(sp2)−H olefination and desilylative vinylation of acyclic enamides have been successfully achieved using vinylsilanes as coupling reagents. The reaction demonstrates effectiveness with a wide range of substrates, exhibiting high tolerance towards various functional groups. This protocol offers a practical approach for the synthesis of two kinds of dienamides, which were obtained in moderate to good yields with high stereoselectivity in both instances. Mechanistically, the β-C(sp2)−H activation was involved in this approach.
{"title":"Rhodium(III)-catalyzed selective C−H olefination and desilylative vinylation of acyclic enamides with vinylsilanes","authors":"Xiaolan Li , Jie Liu , Ruixin Song , Xuzhong Luo , Haiqing Luo","doi":"10.1016/j.jcat.2025.116051","DOIUrl":"10.1016/j.jcat.2025.116051","url":null,"abstract":"<div><div>Rhodium(III)-catalyzed β-C(sp<sup>2</sup>)−H olefination and desilylative vinylation of acyclic enamides have been successfully achieved using vinylsilanes as coupling reagents. The reaction demonstrates effectiveness with a wide range of substrates, exhibiting high tolerance towards various functional groups. This protocol offers a practical approach for the synthesis of two kinds of dienamides, which were obtained in moderate to good yields with high stereoselectivity in both instances. Mechanistically, the β-C(sp<sup>2</sup>)−H activation was involved in this approach.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"446 ","pages":"Article 116051"},"PeriodicalIF":6.5,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547042","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-04DOI: 10.1016/j.jcat.2025.116055
Yuan Wei , Chao Liu , Tian-Tian Wang , Hong-Yu Wang , Yu-Miao Yang , Gao-Feng Shi , Guo-Ying Wang
The rapid recombination rate of photogenerated charges presents considerable challenges for the rational design of high-performance, stable photocatalysts. In this study, we integrated the characteristics of oxygen doping and heterojunctions into oxygen-doped g-C3N4/BiOCl/Bi24O31Cl10 (OCN/BiOCl/Bi24O31Cl10) using a straightforward impregnation-calcination method. Oxygen doping disrupts the symmetric atomic arrangement in pure-phase samples, optimizing the electronic configuration of active sites at the reaction interface and enhancing the coupling between anions and cations. The introduction of BiOCl, which offers an excellent coordination environment, in conjunction with Bi24O31Cl10, creates a dual-S heterojunction. This structure establishes dual reaction interfaces that facilitate efficient dual electron ’transport channels,’ promoting the rapid transfer of charge carriers among OCN, BiOCl, and Bi24O31Cl10. Experimental results demonstrate that the OCN/BiOCl/Bi24O31Cl10 heterojunction material achieves a degradation efficiency of 96.1 % for 10 mg·L−1 levofloxacin under visible light. Notably, in situ measurements obtained through Kelvin probe force microscopy (KPFM) and density functional theory (DFT) calculations jointly reveal a unique chemical environment and electronic structure arising from the formation of an internal electric field among OCN, BiOCl, and Bi24O31Cl10, thereby providing enhanced pathways for the migration of photogenerated charge carriers. Furthermore, the heterostructure significantly reduces the transport distance of photogenically induced charges and decreases internal transport resistance, thereby improving the separation efficiency of photogenerated electron-hole pairs. This mechanism is crucial for the markedly enhanced photocatalytic degradation performance of OCN, BiOCl, and Bi24O31Cl10 materials. In summary, this work explores the synergistic effects among multiple modifications, providing insights for the precise design of efficient and stable photocatalytic degradation systems.
{"title":"The sandwich-shaped double S-scheme heterojuction OCN/BiOCl/Bi24O31Cl10 efficiently degrades levofloxacin and its charge transfer mechanism","authors":"Yuan Wei , Chao Liu , Tian-Tian Wang , Hong-Yu Wang , Yu-Miao Yang , Gao-Feng Shi , Guo-Ying Wang","doi":"10.1016/j.jcat.2025.116055","DOIUrl":"10.1016/j.jcat.2025.116055","url":null,"abstract":"<div><div>The rapid recombination rate of photogenerated charges presents considerable challenges for the rational design of high-performance, stable photocatalysts. In this study, we integrated the characteristics of oxygen doping and heterojunctions into oxygen-doped g-C<sub>3</sub>N<sub>4</sub>/BiOCl/Bi<sub>24</sub>O<sub>31</sub>Cl<sub>10</sub> (OCN/BiOCl/Bi<sub>24</sub>O<sub>31</sub>Cl<sub>10</sub>) using a straightforward impregnation-calcination method. Oxygen doping disrupts the symmetric atomic arrangement in pure-phase samples, optimizing the electronic configuration of active sites at the reaction interface and enhancing the coupling between anions and cations. The introduction of BiOCl, which offers an excellent coordination environment, in conjunction with Bi<sub>24</sub>O<sub>31</sub>Cl<sub>10</sub>, creates a dual-S heterojunction. This structure establishes dual reaction interfaces that facilitate efficient dual electron ’transport channels,’ promoting the rapid transfer of charge carriers among OCN, BiOCl, and Bi<sub>24</sub>O<sub>31</sub>Cl<sub>10</sub>. Experimental results demonstrate that the OCN/BiOCl/Bi<sub>24</sub>O<sub>31</sub>Cl<sub>10</sub> heterojunction material achieves a degradation efficiency of 96.1 % for 10 mg·L<sup>−1</sup> levofloxacin under visible light. Notably, in situ measurements obtained through Kelvin probe force microscopy (KPFM) and density functional theory (DFT) calculations jointly reveal a unique chemical environment and electronic structure arising from the formation of an internal electric field among OCN, BiOCl, and Bi<sub>24</sub>O<sub>31</sub>Cl<sub>10</sub>, thereby providing enhanced pathways for the migration of photogenerated charge carriers. Furthermore, the heterostructure significantly reduces the transport distance of photogenically induced charges and decreases internal transport resistance, thereby improving the separation efficiency of photogenerated electron-hole pairs. This mechanism is crucial for the markedly enhanced photocatalytic degradation performance of OCN, BiOCl, and Bi<sub>24</sub>O<sub>31</sub>Cl<sub>10</sub> materials. In summary, this work explores the synergistic effects among multiple modifications, providing insights for the precise design of efficient and stable photocatalytic degradation systems.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"446 ","pages":"Article 116055"},"PeriodicalIF":6.5,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143538347","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-03DOI: 10.1016/j.jcat.2025.116054
Zahra Almisbaa , Philippe Sautet
The feedstock of the ammonia decomposition reaction often contains water impurities. Water-induced Co oxidation leads to catalyst deactivation. DFT-based microkinetic simulations of ammonia decomposition and water dissociation reactions are used to understand oxygen poisoning on promoted and unpromoted Co surfaces. Simulations show that catalyst oxidation only occurs at low NH3 conversion and, at higher conversion, the produced H2 reduces the catalyst. Hence, in a typical flow reactor, catalyst oxidation is likely to occur only at the reactor inlet. However, the oxidized zone can slowly propagate along the reactor and impact the catalyst stability. The adsorption of oxygen was stronger on BaO-promoted Co in comparison to pristine Co. However, Co-BaO is more sensitive to H2 pressure and needs a lower ammonia conversion to prevent oxygen poisoning on the surface. This indicates that the BaO promoter plays a role in making the catalyst more resistant to O-induced poisoning during the ammonia decomposition reaction.
{"title":"Effect of water impurities on promoted and unpromoted cobalt-catalysts during the ammonia decomposition reaction","authors":"Zahra Almisbaa , Philippe Sautet","doi":"10.1016/j.jcat.2025.116054","DOIUrl":"10.1016/j.jcat.2025.116054","url":null,"abstract":"<div><div>The feedstock of the ammonia decomposition reaction often contains water impurities. Water-induced Co oxidation leads to catalyst deactivation. DFT-based microkinetic simulations of ammonia decomposition and water dissociation reactions are used to understand oxygen poisoning on promoted and unpromoted Co surfaces. Simulations show that catalyst oxidation only occurs at low NH<sub>3</sub> conversion and, at higher conversion, the produced H<sub>2</sub> reduces the catalyst. Hence, in a typical flow reactor, catalyst oxidation is likely to occur only at the reactor inlet. However, the oxidized zone can slowly propagate along the reactor and impact the catalyst stability. The adsorption of oxygen was stronger on BaO-promoted Co in comparison to pristine Co. However, Co-BaO is more sensitive to H<sub>2</sub> pressure and needs a lower ammonia conversion to prevent oxygen poisoning on the surface. This indicates that the BaO promoter plays a role in making the catalyst more resistant to O-induced poisoning during the ammonia decomposition reaction.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"446 ","pages":"Article 116054"},"PeriodicalIF":6.5,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143538348","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-02DOI: 10.1016/j.jcat.2025.116053
Jia Li , Yang Li , Yingshan Zeng , Yang Liu , Zhengguo Song , Zhi Liu
CO2 photo reduction provides a feasible technique to solve climate issues and promote carbon neutrality. However, the efficiency of CO2 photo reduction is severely depressed by the rapid recombination of photo generated carriers within photo catalysts, restricting the participation of electrons in the reduction process. In this study, we successfully construct a two-dimensional (2D) multilayer internal electric field (IEF) heterostructure by engineering the interface between NiAl-LDH and ZnV2O6 (ZNA). Driven by the IEF, the separation of photo generated electron-hole pairs is significantly enhanced, leading to the increased utilization efficiency of carriers for active sites. The best-performing sample of ZNA-2 achieves a highest CO yield of 695.8 μmol g−1, approximately 30.5-fold higher than that of pristine ZnV2O6. Photo electrochemical measurement and density functional theory (DFT) calculation results reveal that the 2D-2D stacked structure generates multiple interlayer built-in electric fields, which are crucial for enhancing carrier separation and suppressing recombination. Adsorption energy and intermediate COOH* analysis reveal that ZNA-2 significantly lowers the adsorption energy of CO2, promoting its stable adsorption and subsequent conversion. Moreover, the unique 2D multilayer IEF heterostructure greatly facilitates the formation of key intermediate COOH* and the desorption of CO during CO2 photo reduction, leading to high CO activity and selectivity. The present work discloses the unprecedented potential of 2D multilayer IEF heterostructures for efficient CO2 photo reduction, marking a significant advancement over conventional 2D counterparts.
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