Chinese Journal of Catalysis最新文献

英文中文

Understanding the C–C coupling mechanism in electrochemical CO reduction at low CO coverage: Dynamic change in site preference matters

IF 15.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-02-01 DOI: 10.1016/S1872-2067(24)60180-4

Zhe Chen , Tao Wang

A thoroughly mechanistic understanding of the electrochemical CO reduction reaction (eCORR) at the interface is significant for guiding the design of high-performance electrocatalysts. However, unintentionally ignored factors or unreasonable settings during mechanism simulations will result in false positive results between theory and experiment. Herein, we computationally identified the dynamic site preference change of CO adsorption with potentials on Cu(100), which was a previously unnoticed factor but significant to potential-dependent mechanistic studies. Combined with the different lateral interactions among adsorbates, we proposed a new C–C coupling mechanism on Cu(100), better explaining the product distribution at different potentials in experimental eCORR. At low potentials (from –0.4 to –0.6 V_RHE), the CO forms dominant adsorption on the bridge site, which couples with another attractively aggregated CO to form a C–C bond. At medium potentials (from –0.6 to –0.8 V_RHE), the hollow-bound CO becomes dominant but tends to isolate with another adsorbate due to the repulsion, thereby blocking the coupling process. At high potentials (above –0.8 V_RHE), the CHO intermediate is produced from the electroreduction of hollow-CO and favors the attraction with another bridge-CO to trigger C–C coupling, making CHO the major common intermediate for C–C bond formation and methane production. We anticipate that our computationally identified dynamic change in site preference of adsorbates with potentials will bring new opportunities for a better understanding of the potential-dependent electrochemical processes.

{"title":"Understanding the C–C coupling mechanism in electrochemical CO reduction at low CO coverage: Dynamic change in site preference matters","authors":"Zhe Chen , Tao Wang","doi":"10.1016/S1872-2067(24)60180-4","DOIUrl":"10.1016/S1872-2067(24)60180-4","url":null,"abstract":"<div><div>A thoroughly mechanistic understanding of the electrochemical CO reduction reaction (eCORR) at the interface is significant for guiding the design of high-performance electrocatalysts. However, unintentionally ignored factors or unreasonable settings during mechanism simulations will result in false positive results between theory and experiment. Herein, we computationally identified the dynamic site preference change of CO adsorption with potentials on Cu(100), which was a previously unnoticed factor but significant to potential-dependent mechanistic studies. Combined with the different lateral interactions among adsorbates, we proposed a new C–C coupling mechanism on Cu(100), better explaining the product distribution at different potentials in experimental eCORR. At low potentials (from –0.4 to –0.6 V<sub>RHE</sub>), the CO forms dominant adsorption on the bridge site, which couples with another attractively aggregated CO to form a C–C bond. At medium potentials (from –0.6 to –0.8 V<sub>RHE</sub>), the hollow-bound CO becomes dominant but tends to isolate with another adsorbate due to the repulsion, thereby blocking the coupling process. At high potentials (above –0.8 V<sub>RHE</sub>), the CHO intermediate is produced from the electroreduction of hollow-CO and favors the attraction with another bridge-CO to trigger C–C coupling, making CHO the major common intermediate for C–C bond formation and methane production. We anticipate that our computationally identified dynamic change in site preference of adsorbates with potentials will bring new opportunities for a better understanding of the potential-dependent electrochemical processes.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"69 ","pages":"Pages 193-202"},"PeriodicalIF":15.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143549252","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}

引用次数: 0

Linkage engineering in covalent organic frameworks for overall photocatalytic H2O2 synthesis from water and air

IF 15.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-02-01 DOI: 10.1016/S1872-2067(24)60195-6

Jian-Zhou Xiao , Zhi-Hao Zhao , Nan-Nan Zhang, Hong-Tu Che, Xiu Qiao, Guang-Ying Zhang, Xiaoyu Chu, Ya Wang, Hong Dong, Feng-Ming Zhang

Artificial photosynthesis of hydrogen peroxide (H₂O₂) using covalent organic frameworks (COFs) as photocatalysts holds promise for future applications. However, the influence of linkage chemistry on the photoelectrochemical properties and photocatalytic performance of COFs remains a significant challenge. Herein, we designed and synthesized a model system with different linkages, including imine-, amine-, azo-linked COFs, then investigated their photocatalytic activity of overall H₂O₂ production. The photocatalytic results revealed varying activities for H₂O₂ synthesis among these COFs, with the azo-linked TTA-Azo-COF (COF synthesized by 4,4’,4’’-(1,3,5-triazine-2,4,6-triyl)-trianiline and terephthalaldehyde) demonstrating the highest overall H₂O₂ photosynthesis activity of 2516 μmol g^–1 h^–1 in an O₂ atmosphere without any sacrificial agents, which is 6.72 and 2.85 times higher than that of imine-linked TTA-COF and amine-linked TTA-COF-AR, respectively. Furthermore, TTA-Azo-COF maintained a high photosynthesis H₂O₂ activity of 2116 μmol g^–1 h^–1 under an air atmosphere, outperforming most COF-based photocatalytic systems under similar reaction conditions. Further characterizations and density functional theory calculations reveal these various linkages in different COFs result in distinct visible-light absorption, charge transfer capacities and formation energy barriers of key intermediates. This work revealed the significant impact of linkages on COFs and provided comprehensive guidance for the rational design of COFs with tailored linkages to fulfill specific requirements for future applications.

{"title":"Linkage engineering in covalent organic frameworks for overall photocatalytic H2O2 synthesis from water and air","authors":"Jian-Zhou Xiao , Zhi-Hao Zhao , Nan-Nan Zhang, Hong-Tu Che, Xiu Qiao, Guang-Ying Zhang, Xiaoyu Chu, Ya Wang, Hong Dong, Feng-Ming Zhang","doi":"10.1016/S1872-2067(24)60195-6","DOIUrl":"10.1016/S1872-2067(24)60195-6","url":null,"abstract":"<div><div>Artificial photosynthesis of hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) using covalent organic frameworks (COFs) as photocatalysts holds promise for future applications. However, the influence of linkage chemistry on the photoelectrochemical properties and photocatalytic performance of COFs remains a significant challenge. Herein, we designed and synthesized a model system with different linkages, including imine-, amine-, azo-linked COFs, then investigated their photocatalytic activity of overall H<sub>2</sub>O<sub>2</sub> production. The photocatalytic results revealed varying activities for H<sub>2</sub>O<sub>2</sub> synthesis among these COFs, with the azo-linked TTA-Azo-COF (COF synthesized by 4,4’,4’’-(1,3,5-triazine-2,4,6-triyl)-trianiline and terephthalaldehyde) demonstrating the highest overall H<sub>2</sub>O<sub>2</sub> photosynthesis activity of 2516 μmol g<sup>–1</sup> h<sup>–1</sup> in an O<sub>2</sub> atmosphere without any sacrificial agents, which is 6.72 and 2.85 times higher than that of imine-linked TTA-COF and amine-linked TTA-COF-AR, respectively. Furthermore, TTA-Azo-COF maintained a high photosynthesis H<sub>2</sub>O<sub>2</sub> activity of 2116 μmol g<sup>–1</sup> h<sup>–1</sup> under an air atmosphere, outperforming most COF-based photocatalytic systems under similar reaction conditions. Further characterizations and density functional theory calculations reveal these various linkages in different COFs result in distinct visible-light absorption, charge transfer capacities and formation energy barriers of key intermediates. This work revealed the significant impact of linkages on COFs and provided comprehensive guidance for the rational design of COFs with tailored linkages to fulfill specific requirements for future applications.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"69 ","pages":"Pages 219-229"},"PeriodicalIF":15.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143549180","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}

引用次数: 0

Pd-Pt bimetallene for the energy-saving electrochemical hydrogenation of 5-hydroxymethylfurfural

IF 15.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-02-01 DOI: 10.1016/S1872-2067(24)60189-0

Xi-Lai Liu, Wei Zhong, Yu-Fan Jin, Tian-Jiao Wang, Xue Xiao, Pei Chen, Yu Chen, Xuan Ai

The electrochemical hydrogenation (ECH) of 5-hydroxymethylfurfural (HMF) to 2,5-dihydroxymethylfuran (DHMF) represents a pivotal pathway for the electrocatalytic upgrading of biomass-based organic small molecules, offering significant reductions in energy consumption while producing value-added chemicals. The conversion of HMF to DHMF is challenging due to the high reduction potential and complex intermediates of HMF ECH under neutral environment. Also, the total efficiency is hindered by sluggish anodic oxygen evolution reaction (OER) kinetics. Herein, we report a synthesis of highly alloyed Pd-Pt bimetallene (Pd₃Pt₁ BML) for HMF ECH coupled with formic acid oxidation reaction (FAOR). Through a combination of in-situ Raman spectroscopy, electron paramagnetic resonance analysis, and theoretical calculations, we elucidate that the HMF adsorption on Pd atoms, strategically separated by Pt atoms, is weakened compared to pure Pd surfaces. Additionally, Pt atoms serve as crucial providers of active hydrogen to neighboring Pd atoms, synergistically enhancing the reaction kinetics of HMF conversion with a Faradaic efficiency >93%. Meanwhile, the atomically dispersed Pt atoms endow Pd₃Pt₁ BML with high electrochemical performance for the direct pathway of FAOR at the anode. As a result, a FAOR-assisted HMF ECH system equipped with bifunctional Pd₃Pt₁ BML achieves the energy-efficient conversion of HMF to DHMF at electrolysis voltage of 0.72 V at 10 mA cm^–2. This work provides insights into the rational design of bifunctional catalysts featuring two distinct types of active sites for advanced energy electrocatalysis and ECH.

{"title":"Pd-Pt bimetallene for the energy-saving electrochemical hydrogenation of 5-hydroxymethylfurfural","authors":"Xi-Lai Liu, Wei Zhong, Yu-Fan Jin, Tian-Jiao Wang, Xue Xiao, Pei Chen, Yu Chen, Xuan Ai","doi":"10.1016/S1872-2067(24)60189-0","DOIUrl":"10.1016/S1872-2067(24)60189-0","url":null,"abstract":"<div><div>The electrochemical hydrogenation (ECH) of 5-hydroxymethylfurfural (HMF) to 2,5-dihydroxymethylfuran (DHMF) represents a pivotal pathway for the electrocatalytic upgrading of biomass-based organic small molecules, offering significant reductions in energy consumption while producing value-added chemicals. The conversion of HMF to DHMF is challenging due to the high reduction potential and complex intermediates of HMF ECH under neutral environment. Also, the total efficiency is hindered by sluggish anodic oxygen evolution reaction (OER) kinetics. Herein, we report a synthesis of highly alloyed Pd-Pt bimetallene (Pd<sub>3</sub>Pt<sub>1</sub> BML) for HMF ECH coupled with formic acid oxidation reaction (FAOR). Through a combination of <em>in-situ</em> Raman spectroscopy, electron paramagnetic resonance analysis, and theoretical calculations, we elucidate that the HMF adsorption on Pd atoms, strategically separated by Pt atoms, is weakened compared to pure Pd surfaces. Additionally, Pt atoms serve as crucial providers of active hydrogen to neighboring Pd atoms, synergistically enhancing the reaction kinetics of HMF conversion with a Faradaic efficiency >93%. Meanwhile, the atomically dispersed Pt atoms endow Pd<sub>3</sub>Pt<sub>1</sub> BML with high electrochemical performance for the direct pathway of FAOR at the anode. As a result, a FAOR-assisted HMF ECH system equipped with bifunctional Pd<sub>3</sub>Pt<sub>1</sub> BML achieves the energy-efficient conversion of HMF to DHMF at electrolysis voltage of 0.72 V at 10 mA cm<sup>–2</sup>. This work provides insights into the rational design of bifunctional catalysts featuring two distinct types of active sites for advanced energy electrocatalysis and ECH.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"69 ","pages":"Pages 241-248"},"PeriodicalIF":15.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143549181","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}

引用次数: 0

Revealing the regulatory mechanism of built-in electric field in defective mesoporous MIL-125(Ti)@BiOCl S-scheme heterojunctions toward optimized photocatalytic performance

IF 15.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-02-01 DOI: 10.1016/S1872-2067(24)60171-3

Tingting Hu , Panpan Feng , Hongqi Chu , Teng Gao , Fusheng Liu , Wei Zhou

The rational configuration of built-in electric field (IEF) in heterogeneous materials can significantly optimize the band structure to accelerate the separation of photogenerated charge carriers. However, the strength modulation of IEF formed by various materials has an uncertain enhancing effect on the separation of photogenerated carriers. Herein, a mesoporous MIL-125(Ti)@BiOCl S-scheme heterojunction with controllable IEF is prepared by green photoreduction reaction to investigate the relationship between IEF, microstructure, and photocatalytic activity. Moreover, the corresponding results demonstrate the MIL-125(Ti)@BiOCl effectively regulates the IEF strength through controlling the concentration of ligand defects, thereby optimizing the band structure and improving the efficiency of photogenerated charge separation. The optimized IEF significantly enhances the photocatalytic degradation performance of mesoporous MIL-125(Ti)-3@BiOCl towards tetracycline, with a k value of 0.07 min^–1, which are approximately 5.5 and 4.7 times greater than that of BiOCl (0.0127 min^–1) and MIL-125(Ti)-3 (0.015 min^–1). These findings provide a new pathway for regulating IEF within MOF-based heterojunctions, and offer new insights into the intrinsic correlations between defect structure, IEF, and photocatalytic activity.

{"title":"Revealing the regulatory mechanism of built-in electric field in defective mesoporous MIL-125(Ti)@BiOCl S-scheme heterojunctions toward optimized photocatalytic performance","authors":"Tingting Hu , Panpan Feng , Hongqi Chu , Teng Gao , Fusheng Liu , Wei Zhou","doi":"10.1016/S1872-2067(24)60171-3","DOIUrl":"10.1016/S1872-2067(24)60171-3","url":null,"abstract":"<div><div>The rational configuration of built-in electric field (IEF) in heterogeneous materials can significantly optimize the band structure to accelerate the separation of photogenerated charge carriers. However, the strength modulation of IEF formed by various materials has an uncertain enhancing effect on the separation of photogenerated carriers. Herein, a mesoporous MIL-125(Ti)@BiOCl S-scheme heterojunction with controllable IEF is prepared by green photoreduction reaction to investigate the relationship between IEF, microstructure, and photocatalytic activity. Moreover, the corresponding results demonstrate the MIL-125(Ti)@BiOCl effectively regulates the IEF strength through controlling the concentration of ligand defects, thereby optimizing the band structure and improving the efficiency of photogenerated charge separation. The optimized IEF significantly enhances the photocatalytic degradation performance of mesoporous MIL-125(Ti)-3@BiOCl towards tetracycline, with a <em>k</em> value of 0.07 min<sup>–1</sup>, which are approximately 5.5 and 4.7 times greater than that of BiOCl (0.0127 min<sup>–1</sup>) and MIL-125(Ti)-3 (0.015 min<sup>–1</sup>). These findings provide a new pathway for regulating IEF within MOF-based heterojunctions, and offer new insights into the intrinsic correlations between defect structure, IEF, and photocatalytic activity.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"69 ","pages":"Pages 123-134"},"PeriodicalIF":15.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143549194","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}

引用次数: 0

Enhanced cofactor recycling and accelerated reaction rate via liquid-liquid phase separation in dual-enzyme condensates

IF 15.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-02-01 DOI: 10.1016/S1872-2067(24)60172-5

Jiaxu Liu , Jiaxin Chen , Xiaoyan Zhang , Daidi Fan , Yunpeng Bai

Enzyme catalysis is a promising way to produce chiral products in a green and sustainable way. However, the high cost of cofactors and their relatively low recycling efficiency hinder the widespread application of enzyme catalysis in industry. In contrast, cofactor regeneration and recycling in cells is highly efficient, mainly due to physical effects caused by the ordered spatial organization of enzymes in vivo. The construction of similar catalytic systems with high cofactor recycling in vitro remains challenging. Here, we present a facile method to generate dual enzyme condensates in vitro based on intrinsically disordered region-mediated liquid-liquid phase separation. Typically, a carbonyl reductase from Serratia marcescens (SmCR_V4) and a glucose dehydrogenase from Bacillus megaterium (BmGDH) were co-localized in the condensates. This resulted in an up to 20-fold increase in cofactor recycling efficiency (substrate converted per cofactor per unit time), and a 3.4-fold increase in space-time yield compared to the free enzyme system. The reaction enhancement was shown to be highly correlated with the degree of condensation of the dual enzymes. Fluorescence confocal microscopy showed that the cofactor, nicotinamide adenine dinucleotide phosphate (NADPH), was enriched between neighboring enzymes during the reaction due to the proximity effect, facilitating its regeneration and recycling within the condensate. In a scaled-up synthesis, the consumption of NADPH was reduced 50-fold compared to industrial biocatalytic standards, while the condensate still maintained efficient product synthesis. Concentrating multiple enzymes in a nano- and micro-condensate to increase the reaction rate may provide a general and inexpensive method for improving cofactor-involved enzymatic reactions.

{"title":"Enhanced cofactor recycling and accelerated reaction rate via liquid-liquid phase separation in dual-enzyme condensates","authors":"Jiaxu Liu , Jiaxin Chen , Xiaoyan Zhang , Daidi Fan , Yunpeng Bai","doi":"10.1016/S1872-2067(24)60172-5","DOIUrl":"10.1016/S1872-2067(24)60172-5","url":null,"abstract":"<div><div>Enzyme catalysis is a promising way to produce chiral products in a green and sustainable way. However, the high cost of cofactors and their relatively low recycling efficiency hinder the widespread application of enzyme catalysis in industry. In contrast, cofactor regeneration and recycling in cells is highly efficient, mainly due to physical effects caused by the ordered spatial organization of enzymes <em>in vivo</em>. The construction of similar catalytic systems with high cofactor recycling <em>in vitro</em> remains challenging. Here, we present a facile method to generate dual enzyme condensates <em>in vitro</em> based on intrinsically disordered region-mediated liquid-liquid phase separation. Typically, a carbonyl reductase from <em>Serratia marcescens</em> (<em>Sm</em>CR<sub>V4</sub>) and a glucose dehydrogenase from <em>Bacillus megaterium</em> (<em>Bm</em>GDH) were co-localized in the condensates. This resulted in an up to 20-fold increase in cofactor recycling efficiency (substrate converted per cofactor per unit time), and a 3.4-fold increase in space-time yield compared to the free enzyme system. The reaction enhancement was shown to be highly correlated with the degree of condensation of the dual enzymes. Fluorescence confocal microscopy showed that the cofactor, nicotinamide adenine dinucleotide phosphate (NADPH), was enriched between neighboring enzymes during the reaction due to the proximity effect, facilitating its regeneration and recycling within the condensate. In a scaled-up synthesis, the consumption of NADPH was reduced 50-fold compared to industrial biocatalytic standards, while the condensate still maintained efficient product synthesis. Concentrating multiple enzymes in a nano- and micro-condensate to increase the reaction rate may provide a general and inexpensive method for improving cofactor-involved enzymatic reactions.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"69 ","pages":"Pages 135-148"},"PeriodicalIF":15.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143549247","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}

引用次数: 0

Mechanism of selective reduction of N2O by CO over Fe-β catalysts studied by in-situ/operando spectroscopy

IF 15.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-02-01 DOI: 10.1016/S1872-2067(24)60161-0

Yucheng Qian , Shunsaku Yasumura , Ningqiang Zhang , Akihiko Anzai , Takashi Toyao , Ken-ichi Shimizu

Selective reduction of N₂O by CO under excess O₂ was effectively catalyzed by Fe(0.9 wt%)-exchanged β zeolite (Fe0.9β) in the temperature range of 250–500 °C. Kinetic experiments showed that the apparent activation energy for N₂O reduction with CO was lower than that for the direct N₂O decomposition, and the rate of N₂O reduction with CO at 300 °C was 16 times higher than that for direct N₂O decomposition. Reaction order analyses showed that CO and N₂O were involved in the kinetically important step, while O₂ was not involved in the important step. At 300 °C, the rate of CO oxidation with 0.1% N₂O was two times higher than that of CO oxidation with 10% O₂. This quantitatively demonstrates the preferential oxidation of CO by N₂O under excess O₂ over Fe0.9β. Operando/in-situ diffuse reflectance ultraviolet-visible spectroscopy showed a redox-based catalytic cycle; α-Fe-O species are reduced by CO to give CO₂ and reduced Fe species, which are then re-oxidized by N₂O to regenerate the α-Fe-O species. The initial rate for the regeneration of α-Fe-O species under 0.1% N₂O was four times higher than that under 10% O₂. This result shows quantitative evidence on the higher reactivity of N₂O than O₂ for the regeneration of α-Fe-O intermediates, providing a fundamental reason why the Fe0.9β catalyst selectively promotes the CO + N₂O reaction under excess O₂ rather than the undesired side reaction of CO + O₂. The mechanistic model was verified by the results of in-situ Fe K-edge X-ray absorption spectroscopy.

{"title":"Mechanism of selective reduction of N2O by CO over Fe-β catalysts studied by in-situ/operando spectroscopy","authors":"Yucheng Qian , Shunsaku Yasumura , Ningqiang Zhang , Akihiko Anzai , Takashi Toyao , Ken-ichi Shimizu","doi":"10.1016/S1872-2067(24)60161-0","DOIUrl":"10.1016/S1872-2067(24)60161-0","url":null,"abstract":"<div><div>Selective reduction of N<sub>2</sub>O by CO under excess O<sub>2</sub> was effectively catalyzed by Fe(0.9 wt%)-exchanged β zeolite (Fe0.9β) in the temperature range of 250–500 °C. Kinetic experiments showed that the apparent activation energy for N<sub>2</sub>O reduction with CO was lower than that for the direct N<sub>2</sub>O decomposition, and the rate of N<sub>2</sub>O reduction with CO at 300 °C was 16 times higher than that for direct N<sub>2</sub>O decomposition. Reaction order analyses showed that CO and N<sub>2</sub>O were involved in the kinetically important step, while O<sub>2</sub> was not involved in the important step. At 300 °C, the rate of CO oxidation with 0.1% N<sub>2</sub>O was two times higher than that of CO oxidation with 10% O<sub>2</sub>. This quantitatively demonstrates the preferential oxidation of CO by N<sub>2</sub>O under excess O<sub>2</sub> over Fe0.9β. <em>Operando/in-situ</em> diffuse reflectance ultraviolet-visible spectroscopy showed a redox-based catalytic cycle; α-Fe-O species are reduced by CO to give CO<sub>2</sub> and reduced Fe species, which are then re-oxidized by N<sub>2</sub>O to regenerate the α-Fe-O species. The initial rate for the regeneration of α-Fe-O species under 0.1% N<sub>2</sub>O was four times higher than that under 10% O<sub>2</sub>. This result shows quantitative evidence on the higher reactivity of N<sub>2</sub>O than O<sub>2</sub> for the regeneration of α-Fe-O intermediates, providing a fundamental reason why the Fe0.9β catalyst selectively promotes the CO + N<sub>2</sub>O reaction under excess O<sub>2</sub> rather than the undesired side reaction of CO + O<sub>2</sub>. The mechanistic model was verified by the results of <em>in-situ</em> Fe K-edge X-ray absorption spectroscopy.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"69 ","pages":"Pages 185-192"},"PeriodicalIF":15.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143549251","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}

引用次数: 0

Switching electronic effects of UiO-67-Pd using fluorinated ligands for catalytic oxidative arylation of bio-based furfuryl alcohol

IF 15.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-02-01 DOI: 10.1016/S1872-2067(24)60207-X

Dongwen Guo, Guohui Zeng, Jinxing Long, Biaolin Yin

An efficient and novel approach is proposed for oxidative arylation of bio-based furfuryl alcohol (FA) to aryl furans (AFs), a versatile monomer of photoelectric materials, in the presence of UiO-67-Pd(F) with phenanthroline/ bipyridine, and poly-F substituted phenyl ligands as the mixture linkers. The results of control experiments and theoretical calculations reveal that the –F on the phenyl linkers efficiently tunes the electron-deficient nature of Pd through the Zr₆ clusters bridges, which favors the adsorption and activation of the furan ring. Furthermore, the conjugation of different nitrogen-containing ligands facilitates Pd coordination for the Heck-type insertion and subsequent electrophilic palladation, respectively. As a result, the oxidative arylation of FA derivatives is substantially enhanced because of these electronic and steric synergistic effects. Under the optimized conditions, 72.2% FA conversion and 74.8% mono aryl furan (MAF) selectivity are shown in the Heck-type insertion. Meanwhile, 85.3% of MAF is converted, affording 74.8% selectivity of final product (AFs) in the subsequent electrophilic palladation reaction. This process efficiency is remarkably higher than that with homogeneous catalysts. In addition, furan-benzene polymer obtained from the halogen-free synthesis catalyzed by UiO-67-Pd(F) show significantly better properties than that from conventional Suzuki coupling method. Therefore, the present work provides a new insight for useful AFs synthesis by oxidative arylation of bio-furan via rational tunning the metal center micro-environment of heterogeneous catalyst.

{"title":"Switching electronic effects of UiO-67-Pd using fluorinated ligands for catalytic oxidative arylation of bio-based furfuryl alcohol","authors":"Dongwen Guo, Guohui Zeng, Jinxing Long, Biaolin Yin","doi":"10.1016/S1872-2067(24)60207-X","DOIUrl":"10.1016/S1872-2067(24)60207-X","url":null,"abstract":"<div><div>An efficient and novel approach is proposed for oxidative arylation of bio-based furfuryl alcohol (FA) to aryl furans (AFs), a versatile monomer of photoelectric materials, in the presence of UiO-67-Pd(F) with phenanthroline/ bipyridine, and poly-F substituted phenyl ligands as the mixture linkers. The results of control experiments and theoretical calculations reveal that the –F on the phenyl linkers efficiently tunes the electron-deficient nature of Pd through the Zr<sub>6</sub> clusters bridges, which favors the adsorption and activation of the furan ring. Furthermore, the conjugation of different nitrogen-containing ligands facilitates Pd coordination for the Heck-type insertion and subsequent electrophilic palladation, respectively. As a result, the oxidative arylation of FA derivatives is substantially enhanced because of these electronic and steric synergistic effects. Under the optimized conditions, 72.2% FA conversion and 74.8% mono aryl furan (MAF) selectivity are shown in the Heck-type insertion. Meanwhile, 85.3% of MAF is converted, affording 74.8% selectivity of final product (AFs) in the subsequent electrophilic palladation reaction. This process efficiency is remarkably higher than that with homogeneous catalysts. In addition, furan-benzene polymer obtained from the halogen-free synthesis catalyzed by UiO-67-Pd(F) show significantly better properties than that from conventional Suzuki coupling method. Therefore, the present work provides a new insight for useful AFs synthesis by oxidative arylation of bio-furan <em>via</em> rational tunning the metal center micro-environment of heterogeneous catalyst.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"69 ","pages":"Pages 230-240"},"PeriodicalIF":15.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143549253","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}

引用次数: 0

The mechanism of OER activity and stability enhancement in acid by atomically doped iridium in γ-MnO2

IF 15.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-02-01 DOI: 10.1016/S1872-2067(24)60201-9

Yimeng Sun , Jun Chen , Lin Liu , Haibo Chi , Hongxian Han

Construction of iridium (Ir) based active sites on certain acid stable supports now is a general strategy for the development of low-Ir OER catalysts. Atomically doped Ir in the lattice of acid stable γ-MnO₂ has been recently achieved, which shows high activity and stability though Ir usage was reduced more than 95% than that in current commercial proton exchange membrane water electrolyzer (PEMWE). However, the activity and stability enhancement by Ir doping in γ-MnO₂ still remains elusive. Herein, high dispersion of iridium (up to 1.37 atom%) doping in the lattice of γ-MnO₂ has been achieved by optimizing the thermal decomposition of the iridium precursors. Benefiting from atomic dispersive doping of Ir, the optimized Ir-MnO₂ catalyst shows high OER activity, as it has turnover frequency of 0.655 s^–1 at an overpotential of 300 mV in 0.5 mol L⁻¹ H₂SO₄. The catalyst also shows high stability, as it can sustainably work at 100 mA cm⁻² for 24 h. Experimental and theoretical studies reveal that Ir is preferentially doped into β phase rather than R phase, and the Ir site is the active site for OER. The OER active site is postulated to be Ir⁵⁺-O(H)-Mn³⁺ unit structure on the surface. Furthermore, Ir doping changes the potential determining step from the formation of O* to the formation of *OOH, emphasizing the promoting effect toward OER derived from Ir sites. This work not only demonstrates the possibility of achieving atomic-level doping of Ir on the surface of a support to dramatically reduce Ir usage, but also, more importantly, reveals the mechanism behind accounting for the stability and activity enhancement by Ir doping. These important findings may serve as valuable guidance for further development of more efficient, stable and cost-effective low Ir-based OER catalysts for PEMWE.

{"title":"The mechanism of OER activity and stability enhancement in acid by atomically doped iridium in γ-MnO2","authors":"Yimeng Sun , Jun Chen , Lin Liu , Haibo Chi , Hongxian Han","doi":"10.1016/S1872-2067(24)60201-9","DOIUrl":"10.1016/S1872-2067(24)60201-9","url":null,"abstract":"<div><div>Construction of iridium (Ir) based active sites on certain acid stable supports now is a general strategy for the development of low-Ir OER catalysts. Atomically doped Ir in the lattice of acid stable γ-MnO<sub>2</sub> has been recently achieved, which shows high activity and stability though Ir usage was reduced more than 95% than that in current commercial proton exchange membrane water electrolyzer (PEMWE). However, the activity and stability enhancement by Ir doping in γ-MnO<sub>2</sub> still remains elusive. Herein, high dispersion of iridium (up to 1.37 atom%) doping in the lattice of γ-MnO<sub>2</sub> has been achieved by optimizing the thermal decomposition of the iridium precursors. Benefiting from atomic dispersive doping of Ir, the optimized Ir-MnO<sub>2</sub> catalyst shows high OER activity, as it has turnover frequency of 0.655 s<sup>–1</sup> at an overpotential of 300 mV in 0.5 mol L<sup>−1</sup> H<sub>2</sub>SO<sub>4</sub>. The catalyst also shows high stability, as it can sustainably work at 100 mA cm<sup>−2</sup> for 24 h. Experimental and theoretical studies reveal that Ir is preferentially doped into <em>β</em> phase rather than R phase, and the Ir site is the active site for OER. The OER active site is postulated to be Ir<sup>5+</sup>-O(H)-Mn<sup>3+</sup> unit structure on the surface. Furthermore, Ir doping changes the potential determining step from the formation of O* to the formation of *OOH, emphasizing the promoting effect toward OER derived from Ir sites. This work not only demonstrates the possibility of achieving atomic-level doping of Ir on the surface of a support to dramatically reduce Ir usage, but also, more importantly, reveals the mechanism behind accounting for the stability and activity enhancement by Ir doping. These important findings may serve as valuable guidance for further development of more efficient, stable and cost-effective low Ir-based OER catalysts for PEMWE.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"69 ","pages":"Pages 99-110"},"PeriodicalIF":15.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143549246","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}

引用次数: 0

Boosting hydrogen peroxide photosynthesis via a 1D/2D S-scheme heterojunction constructed by a covalent triazine framework with dual O2 reduction centers

IF 15.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-02-01 DOI: 10.1016/S1872-2067(24)60210-X

Bingquan Xia , Gaoxiong Liu , Kun Fan , Rundong Chen , Xin Liu , Laiquan Li

Emerging as lamellar materials, covalent triazine frameworks (CTFs) exhibited great potential for photocatalysis, but their photocatalytic performance is always hindered by the prone recombination of photogenerated carriers. To overcome this obstacle, a 1D/2D step-scheme (S-scheme) heterojunction is constructed for photocatalytic synthesis of H₂O₂. The S-scheme heterojunction fabricated with CTF and ZnO effectively enhances light absorption, redox capabilities, and charge carrier separation and transfer. In particular, the CTF is decorated with benzothiadiazole and triazine groups as dual O₂ reduction active centers, boosting photocatalytic H₂O₂ production. The optimal ZC-10 hybrid delivers a maximum H₂O₂ generation rate of 12000 μmol g^–1 h^–1, 10.3 and 164 times higher than those of zinc oxide nanorods and CTFs, respectively. Moreover, the charge transfer mechanism in the S-scheme heterojunction is well investigated with in situ spectroscopic measurements and theoretical calculations.

{"title":"Boosting hydrogen peroxide photosynthesis via a 1D/2D S-scheme heterojunction constructed by a covalent triazine framework with dual O2 reduction centers","authors":"Bingquan Xia , Gaoxiong Liu , Kun Fan , Rundong Chen , Xin Liu , Laiquan Li","doi":"10.1016/S1872-2067(24)60210-X","DOIUrl":"10.1016/S1872-2067(24)60210-X","url":null,"abstract":"<div><div>Emerging as lamellar materials, covalent triazine frameworks (CTFs) exhibited great potential for photocatalysis, but their photocatalytic performance is always hindered by the prone recombination of photogenerated carriers. To overcome this obstacle, a 1D/2D step-scheme (S-scheme) heterojunction is constructed for photocatalytic synthesis of H<sub>2</sub>O<sub>2</sub>. The S-scheme heterojunction fabricated with CTF and ZnO effectively enhances light absorption, redox capabilities, and charge carrier separation and transfer. In particular, the CTF is decorated with benzothiadiazole and triazine groups as dual O<sub>2</sub> reduction active centers, boosting photocatalytic H<sub>2</sub>O<sub>2</sub> production. The optimal ZC-10 hybrid delivers a maximum H<sub>2</sub>O<sub>2</sub> generation rate of 12000 μmol g<sup>–1</sup> h<sup>–1</sup>, 10.3 and 164 times higher than those of zinc oxide nanorods and CTFs, respectively. Moreover, the charge transfer mechanism in the S-scheme heterojunction is well investigated with in situ spectroscopic measurements and theoretical calculations.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"69 ","pages":"Pages 315-326"},"PeriodicalIF":15.7,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143549196","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}

引用次数: 0

Commercialization of electrochemical CO2 reduction: HCOOH pathway versus CO pathway

IF 15.7 1区化学 Q1 CHEMISTRY, APPLIED

Chinese Journal of Catalysis

Pub Date : 2025-02-01 DOI: 10.1016/S1872-2067(24)60202-0

Zhaoyang Chen , Qingtian Zhong , Qiqige Wulan, Yuan Ji, Chunxiao Liu, Xu Li, Tingting Zheng, Qiu Jiang, Chuan Xia

The objective of electrochemical CO₂ reduction technologies (ECRs) is notably audacious: to revolutionize the market by generating fuel and essential chemicals at a more competitive price than petrochemicals can offer, all while prioritizing environmental sustainability. To expedite the commercialization of ECR technology, we discuss here how ECR can reshape the industry landscape through 2e⁻ pathways.

引用次数: 0

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