Pub Date : 2025-08-01DOI: 10.1016/S1872-5813(25)60533-0
Ting HUANG , Bing FENG , Peipei LU , Zhongliang ZHANG , Qi NIU , Zonghu MA , Kai LI , Qiang LU
To optimize the CO2 adsorption performance of carbon materials, this study proposed a preparation method for biomass-based porous carbon through hydrothermal carbonization coupled with nitrogen source optimization and K2CO3 activation. The effects of different nitrogen sources (urea, piperazine, melamine, and polyaniline) and activation temperatures on the physicochemical features and CO2 adsorption characteristics of the porous carbons were systematically investigated. The results indicated that different nitrogen sources showed varying impacts on the CO2 uptake of porous carbons, and not all nitrogen sources enhanced the adsorption performance. The urea and piperazine doped porous carbons exhibited relatively low nitrogen contents and specific surface areas. Whereas the melamine doped carbons showed higher nitrogen contents and specific surface areas, but lacked narrow micropores, limiting their CO2 adsorption performance. In contrast, PAC-700, prepared using polyaniline as nitrogen source, featured a well-developed pore structure, abundant narrow micropores and pyrrolic-N groups, endowing it with enhanced CO2 adsorption capability. At 0 °C/1 bar and 25 °C/1 bar, the CO2 uptake of PAC-700 reached 6.85 and 4.64 mmol/g, respectively. Additionally, PAC-700 maintained a CO2 uptake retention ratio of 99% after 5 adsorption-desorption cycles and exhibited good CO2/N2 selectivity of 22.4−51.6. These findings highlighted the advantageous CO2 adsorption performance of PAC-700, indicating its substantial application potential in the domain of carbon capture.
{"title":"Hydrothermal N-doping assisted synthesis of poplar sawdust-derived porous carbons for carbon capture","authors":"Ting HUANG , Bing FENG , Peipei LU , Zhongliang ZHANG , Qi NIU , Zonghu MA , Kai LI , Qiang LU","doi":"10.1016/S1872-5813(25)60533-0","DOIUrl":"10.1016/S1872-5813(25)60533-0","url":null,"abstract":"<div><div>To optimize the CO<sub>2</sub> adsorption performance of carbon materials, this study proposed a preparation method for biomass-based porous carbon through hydrothermal carbonization coupled with nitrogen source optimization and K<sub>2</sub>CO<sub>3</sub> activation. The effects of different nitrogen sources (urea, piperazine, melamine, and polyaniline) and activation temperatures on the physicochemical features and CO<sub>2</sub> adsorption characteristics of the porous carbons were systematically investigated. The results indicated that different nitrogen sources showed varying impacts on the CO<sub>2</sub> uptake of porous carbons, and not all nitrogen sources enhanced the adsorption performance. The urea and piperazine doped porous carbons exhibited relatively low nitrogen contents and specific surface areas. Whereas the melamine doped carbons showed higher nitrogen contents and specific surface areas, but lacked narrow micropores, limiting their CO<sub>2</sub> adsorption performance. In contrast, PAC-700, prepared using polyaniline as nitrogen source, featured a well-developed pore structure, abundant narrow micropores and pyrrolic-N groups, endowing it with enhanced CO<sub>2</sub> adsorption capability. At 0 °C/1 bar and 25 °C/1 bar, the CO<sub>2</sub> uptake of PAC-700 reached 6.85 and 4.64 mmol/g, respectively. Additionally, PAC-700 maintained a CO<sub>2</sub> uptake retention ratio of 99% after 5 adsorption-desorption cycles and exhibited good CO<sub>2</sub>/N<sub>2</sub> selectivity of 22.4−51.6. These findings highlighted the advantageous CO<sub>2</sub> adsorption performance of PAC-700, indicating its substantial application potential in the domain of carbon capture.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 8","pages":"Pages 1191-1202"},"PeriodicalIF":0.0,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144886579","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-08-01DOI: 10.1016/S1872-5813(25)60544-5
Lei ZHANG , Mingxin LIU , Yisong ZHENG , Guochao AN , Jiao HAN , Caishun ZHANG , Zhixian GAO
Using CeO2, ZrO2, γ-Al2O3, AlO(OH) as the carrier and RuCl3 as the ruthenium source, the Ru/MxOy catalyst was prepared by deposition-precipitation method. Through XRD, BET, H2-TPR, XPS and other characterization methods, combined with high flux methanol steam reforming hydrogen production reaction evaluation, the influence of different carriers on the catalytic performance of Ru/MxOy catalyst was investigated. The experimental results showed that the difference of the interaction between RuOx and the carrier, as well as the presence or absence of oxygen vacancy, showed a significant carrier effect. The Ru/CeO2 catalyst prepared with CeO2 as the carrier has good dispersibility of RuOx, strong interaction between RuOx and the carrier, oxygen vacancy, and good catalytic activity. At the reaction temperature of 420 ℃, the molar ratio of water to alcohol is 1.2, and the space velocity of methanol water mass is 6 h−1, the methanol conversion rate is 88.64%, and the catalytic activity is good at high flux.
{"title":"Carrier effect of Ru/MxOy catalyzed methanol steam reforming reaction","authors":"Lei ZHANG , Mingxin LIU , Yisong ZHENG , Guochao AN , Jiao HAN , Caishun ZHANG , Zhixian GAO","doi":"10.1016/S1872-5813(25)60544-5","DOIUrl":"10.1016/S1872-5813(25)60544-5","url":null,"abstract":"<div><div>Using CeO<sub>2</sub>, ZrO<sub>2</sub>, <em>γ</em>-Al<sub>2</sub>O<sub>3</sub>, AlO(OH) as the carrier and RuCl<sub>3</sub> as the ruthenium source, the Ru/M<sub><em>x</em></sub>O<sub><em>y</em></sub> catalyst was prepared by deposition-precipitation method. Through XRD, BET, H<sub>2</sub>-TPR, XPS and other characterization methods, combined with high flux methanol steam reforming hydrogen production reaction evaluation, the influence of different carriers on the catalytic performance of Ru/M<sub><em>x</em></sub>O<sub><em>y</em></sub> catalyst was investigated. The experimental results showed that the difference of the interaction between RuO<sub><em>x</em></sub> and the carrier, as well as the presence or absence of oxygen vacancy, showed a significant carrier effect. The Ru/CeO<sub>2</sub> catalyst prepared with CeO<sub>2</sub> as the carrier has good dispersibility of RuO<sub><em>x</em></sub>, strong interaction between RuO<sub><em>x</em></sub> and the carrier, oxygen vacancy, and good catalytic activity. At the reaction temperature of 420 ℃, the molar ratio of water to alcohol is 1.2, and the space velocity of methanol water mass is 6 h<sup>−1</sup>, the methanol conversion rate is 88.64%, and the catalytic activity is good at high flux.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 8","pages":"Pages 1233-1242"},"PeriodicalIF":0.0,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144886499","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-01DOI: 10.1016/S1872-5813(24)60523-2
Kunyun WU , Shiyu SU , Xia WANG , Yingqi ZHAO , Caishun ZHANG , Jiao HAN , Yuehong ZHANG , Xiaoning HOU , Lei ZHANG , Zhixian GAO
In this paper, three methods, namely hydrothermal, Al modification and acid washing, were used to modify Cu-Al spinel catalyst, and then the catalysts were characterized by XRD, BET, H2-TPR and XPS techniques. In conjunction with the performances of methanol steam reforming, the effects of surface composition and structure on the catalytic behaviors of the sustained release process were investigated. The results showed that new crystalline phase formed and surface species changed after the hydrothermal treatment, while Al-modification and acid-treated catalysts didn't change the crystalline phase composition, but the surface Al/Cu ratio and the distribution of Cu species changed. Based on the characterization data of the released Cu, it could be inferred that all the three treatments led to variations of the microscopic surface structure, thus exhibiting different sustained release catalytic behaviors. Specifically, the hydrothermal treatment enhanced the catalytic activity, while Al-modification and acid-treated catalysts showed inferior activity but showing obvious sustained release behavior. The findings of this paper provide a basis for further studies on the surface modification of the Cu-Al spinel catalyst.
{"title":"Characteristics of the sustained release of Cu-Al spinel pretreated by different methods for hydrogen production from methanol steam reforming","authors":"Kunyun WU , Shiyu SU , Xia WANG , Yingqi ZHAO , Caishun ZHANG , Jiao HAN , Yuehong ZHANG , Xiaoning HOU , Lei ZHANG , Zhixian GAO","doi":"10.1016/S1872-5813(24)60523-2","DOIUrl":"10.1016/S1872-5813(24)60523-2","url":null,"abstract":"<div><div>In this paper, three methods, namely hydrothermal, Al modification and acid washing, were used to modify Cu-Al spinel catalyst, and then the catalysts were characterized by XRD, BET, H<sub>2</sub>-TPR and XPS techniques. In conjunction with the performances of methanol steam reforming, the effects of surface composition and structure on the catalytic behaviors of the sustained release process were investigated. The results showed that new crystalline phase formed and surface species changed after the hydrothermal treatment, while Al-modification and acid-treated catalysts didn't change the crystalline phase composition, but the surface Al/Cu ratio and the distribution of Cu species changed. Based on the characterization data of the released Cu, it could be inferred that all the three treatments led to variations of the microscopic surface structure, thus exhibiting different sustained release catalytic behaviors. Specifically, the hydrothermal treatment enhanced the catalytic activity, while Al-modification and acid-treated catalysts showed inferior activity but showing obvious sustained release behavior. The findings of this paper provide a basis for further studies on the surface modification of the Cu-Al spinel catalyst.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 7","pages":"Pages 1050-1060"},"PeriodicalIF":0.0,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144696624","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-01DOI: 10.1016/S1872-5813(24)60528-1
Jinting HAN , Xinging MENG , Gengqian WANG , Xiaocong SUN , Yali TIAN , Xiaohu HE , Xuanbing QIU , Chuanliang LI , Yuanyang WANG
An on-line detection system for detecting hydrogen cyanide (HCN) of polyacrylonitrile (PAN) pyrolysis based on thermogravimetric-tunable diode laser absorption spectroscopy (TG-TDLAS) is constructed. Taking advantage of the characteristics that HCN has a relatively high absorption intensity at a wavelength of 1531.156 nm and that common gases in the background gas in this wavelength band cause less interference, concentration of HCN is obtained by demodulating the second harmonic of the absorption signal. By a high-precision flow controller and dilution proportioning with 99.99% standard nitrogen gas, five standard gases in the range of 20×10–6–100×10–6 mol/mol are obtained. The demodulated second harmonic signal is linearly fitted with a correlation coefficient of 0.9975. Effects of four different relative molecular mass of PANs and three heating rates on the pyrolysis were analyzed. The relationship between sample weight loss rate and amount of HCN released was studied to explore non-isothermal pyrolysis kinetics of PAN. A three-stage pyrolysis kinetic model is established by dividing pyrolysis temperature stages, and the activation energies and frequency factors of different relative molecular mass at different heating rates are calculated, respectively. The results show that the higher the molecular weight and the higher the viscosity, the smaller the HCN release. HCN release and PAN weight loss rate in the first and third stages are larger than that in the second stage. It provides a certain experimental basis for further study of HCN generation mechanism in PAN pyrolysis.
{"title":"Evolution of hydrogen cyanide generated from polyacrylonitrile pyrolysis based on TG-LAS","authors":"Jinting HAN , Xinging MENG , Gengqian WANG , Xiaocong SUN , Yali TIAN , Xiaohu HE , Xuanbing QIU , Chuanliang LI , Yuanyang WANG","doi":"10.1016/S1872-5813(24)60528-1","DOIUrl":"10.1016/S1872-5813(24)60528-1","url":null,"abstract":"<div><div>An on-line detection system for detecting hydrogen cyanide (HCN) of polyacrylonitrile (PAN) pyrolysis based on thermogravimetric-tunable diode laser absorption spectroscopy (TG-TDLAS) is constructed. Taking advantage of the characteristics that HCN has a relatively high absorption intensity at a wavelength of 1531.156 nm and that common gases in the background gas in this wavelength band cause less interference, concentration of HCN is obtained by demodulating the second harmonic of the absorption signal. By a high-precision flow controller and dilution proportioning with 99.99% standard nitrogen gas, five standard gases in the range of 20×10<sup>–6</sup>–100×10<sup>–6</sup> mol/mol are obtained. The demodulated second harmonic signal is linearly fitted with a correlation coefficient of 0.9975. Effects of four different relative molecular mass of PANs and three heating rates on the pyrolysis were analyzed. The relationship between sample weight loss rate and amount of HCN released was studied to explore non-isothermal pyrolysis kinetics of PAN. A three-stage pyrolysis kinetic model is established by dividing pyrolysis temperature stages, and the activation energies and frequency factors of different relative molecular mass at different heating rates are calculated, respectively. The results show that the higher the molecular weight and the higher the viscosity, the smaller the HCN release. HCN release and PAN weight loss rate in the first and third stages are larger than that in the second stage. It provides a certain experimental basis for further study of HCN generation mechanism in PAN pyrolysis.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 7","pages":"Pages 1112-1122"},"PeriodicalIF":0.0,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144696671","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hydrogen-enriched ironmaking presents a promising approach to mitigate coke consumption and carbon emission in blast furnace (BF) operations. This work investigated the relationship between the structural features of cokes and their reactivity towards solution loss (SL), especially under hydrogen-enriched atmospheres. Six cokes were characterized, and their SL behaviors were examined under varying atmospheres to elucidate the effects of hydrogen enrichment. The results indicate that an increase in fixed carbon content leads to a decrease in the coke reactivity index (CRI) and an increase in coke strength after reaction (CSR), in the CO2 atmosphere, the CSR of coke increases from 35.76%−62.83%, while in the 90CO2/10H2 atmosphere, the CSR of coke increases from 65.67%−84.09%. There is a good linear relationship between CRI and microcrystalline structure parameters of coke. Cokes with larger crystalline size, lower amorphous content, and smaller optical texture index (OTI) values show enhanced resistance to degradation and maintain structural integrity in BF. Kinetic analysis performed with the shifted-modified-random pore model (S-MRPM) reveals that alterations in pore structure and intrinsic mineral composition significantly influence the reaction rate. The introduction of a small amount of water vapor raises SL rates, whereas a minor addition of hydrogen (<10%) decelerates SL due to its incomplete conversion to water vapor and the reduced partial pressure of the gasifying agent. Thermodynamic calculations also indicate that the introduced hydrogen does not convert into the same fraction of water vapor. The shift from chemical reaction control to gas diffusion control as the rate-determining step with rising temperatures during SL process was confirmed, and the introduction of hydrogen does not notably alter SL behavior. This result demonstrated that introducing a small amount of hydrogen (<10%) can mitigate SL rates, thereby enhancing coke strength and reducing coke consumption and carbon emissions.
{"title":"Solution loss behavior of cokes and its kinetics under hydrogen-enriched atmosphere","authors":"Jingchong YAN, Kaixiang MA, Rong GE, Zhiping LEI, Zhanku LI, Weidong ZHANG, Shibiao REN, Zhicai WANG, Hengfu SHUI","doi":"10.1016/S1872-5813(25)60532-9","DOIUrl":"10.1016/S1872-5813(25)60532-9","url":null,"abstract":"<div><div>Hydrogen-enriched ironmaking presents a promising approach to mitigate coke consumption and carbon emission in blast furnace (BF) operations. This work investigated the relationship between the structural features of cokes and their reactivity towards solution loss (SL), especially under hydrogen-enriched atmospheres. Six cokes were characterized, and their SL behaviors were examined under varying atmospheres to elucidate the effects of hydrogen enrichment. The results indicate that an increase in fixed carbon content leads to a decrease in the coke reactivity index (CRI) and an increase in coke strength after reaction (CSR), in the CO<sub>2</sub> atmosphere, the CSR of coke increases from 35.76%−62.83%, while in the 90CO<sub>2</sub>/10H<sub>2</sub> atmosphere, the CSR of coke increases from 65.67%−84.09%. There is a good linear relationship between CRI and microcrystalline structure parameters of coke. Cokes with larger crystalline size, lower amorphous content, and smaller optical texture index (OTI) values show enhanced resistance to degradation and maintain structural integrity in BF. Kinetic analysis performed with the shifted-modified-random pore model (S-MRPM) reveals that alterations in pore structure and intrinsic mineral composition significantly influence the reaction rate. The introduction of a small amount of water vapor raises SL rates, whereas a minor addition of hydrogen (<10%) decelerates SL due to its incomplete conversion to water vapor and the reduced partial pressure of the gasifying agent. Thermodynamic calculations also indicate that the introduced hydrogen does not convert into the same fraction of water vapor. The shift from chemical reaction control to gas diffusion control as the rate-determining step with rising temperatures during SL process was confirmed, and the introduction of hydrogen does not notably alter SL behavior. This result demonstrated that introducing a small amount of hydrogen (<10%) can mitigate SL rates, thereby enhancing coke strength and reducing coke consumption and carbon emissions.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 7","pages":"Pages 1123-1136"},"PeriodicalIF":0.0,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144696672","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-01DOI: 10.1016/S1872-5813(24)60529-3
Wen LI , Shuaishuai ZHU , Zengneng MA , Yi ZHENG , Jing ZHANG
The p-type semiconductor antimony selenide (Sb2Se3), with high absorption coefficient (> 105 cm–1) in the visible region, band gap of about 1.1 eV, simple binary composition with fixed orthogonal phase and low toxicity, is an excellent light absorber. So, it has been applied in photocatalytic (PEC) solar water splitting to produce hydrogen in recent years due to the excellent photoelectrochemical properties. In this work, the structure and properties of Sb2Se3 are outlined, focus on the development of Sb2Se3-based photoelectrocathodes for PEC water splitting to improve the efficiency of solar hydrogen production (STH) through morphology control, heterostructure construction, heteroatom doping and promotor modification. Then, future directions of the research for Sb2Se3-based photocathodes are discuss.
{"title":"Research progress on antimony selenide photocathode for photocatalytic water splitting","authors":"Wen LI , Shuaishuai ZHU , Zengneng MA , Yi ZHENG , Jing ZHANG","doi":"10.1016/S1872-5813(24)60529-3","DOIUrl":"10.1016/S1872-5813(24)60529-3","url":null,"abstract":"<div><div>The <em>p</em>-type semiconductor antimony selenide (Sb<sub>2</sub>Se<sub>3</sub>), with high absorption coefficient (> 10<sup>5</sup> cm<sup>–1</sup>) in the visible region, band gap of about 1.1 eV, simple binary composition with fixed orthogonal phase and low toxicity, is an excellent light absorber. So, it has been applied in photocatalytic (PEC) solar water splitting to produce hydrogen in recent years due to the excellent photoelectrochemical properties. In this work, the structure and properties of Sb<sub>2</sub>Se<sub>3</sub> are outlined, focus on the development of Sb<sub>2</sub>Se<sub>3</sub>-based photoelectrocathodes for PEC water splitting to improve the efficiency of solar hydrogen production (STH) through morphology control, heterostructure construction, heteroatom doping and promotor modification. Then, future directions of the research for Sb<sub>2</sub>Se<sub>3</sub>-based photocathodes are discuss.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 7","pages":"Pages 1025-1037"},"PeriodicalIF":0.0,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144696845","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-01DOI: 10.1016/S1872-5813(25)60535-4
Yapeng BEI , Xing YU , Xianni BU , Yuhan SUN , Peng GAO
Direct hydrogenation of CO2 to aromatics via the methanol-mediated route over an oxide-zeolite bifunctional catalyst has received considerable attention in recent years. However, the activation of CO2 at mild condition remains a great challenge, as it needs to conquer a high activation energy barrier due to the chemical inertness of CO2. Herein, ZnZrOx oxides were modified by a series of transition metals (M = Fe, Cu, Co, Ni) and the modified M-ZnZrOx oxides were further used together with the commercial ZSM-5 zeolite to comprise the bifunctional M-ZnZrOx/ZSM-5 composite catalysts for the direct hydrogenation of CO2 to aromatics. The results indicate that the iron-modified Fe-ZnZrOx/ZSM-5 catalysts have abundant oxygen vacancies which are active for the transformation CO2 to aromatics; under 275 °C, H2/CO2 = 3, and a space velocity of 600 mL/(g·h), the Fe(4)-ZnZrOx/ZSM-5 catalyst with an Fe mass fraction of 4% achieves a selectivity of 80.4% to aromatics, where tetramethylbenzene accounts for more than 70.4%, with a single-pass CO2 conversion of 5.6%. A further increase of the Fe content to 8% can even improve the selectivity to aromatics (85.0%). Such observation should be useful for the design of industrial catalysts efficient for the direct conversion of CO2 to aromatics.
{"title":"Modified ZnZrOx coupled with ZSM-5 as the catalyst for the hydrogenation of CO2 to aromatics","authors":"Yapeng BEI , Xing YU , Xianni BU , Yuhan SUN , Peng GAO","doi":"10.1016/S1872-5813(25)60535-4","DOIUrl":"10.1016/S1872-5813(25)60535-4","url":null,"abstract":"<div><div>Direct hydrogenation of CO<sub>2</sub> to aromatics via the methanol-mediated route over an oxide-zeolite bifunctional catalyst has received considerable attention in recent years. However, the activation of CO<sub>2</sub> at mild condition remains a great challenge, as it needs to conquer a high activation energy barrier due to the chemical inertness of CO<sub>2</sub>. Herein, ZnZrO<sub><em>x</em></sub> oxides were modified by a series of transition metals (M = Fe, Cu, Co, Ni) and the modified M-ZnZrO<sub><em>x</em></sub> oxides were further used together with the commercial ZSM-5 zeolite to comprise the bifunctional M-ZnZrO<sub><em>x</em></sub>/ZSM-5 composite catalysts for the direct hydrogenation of CO<sub>2</sub> to aromatics. The results indicate that the iron-modified Fe-ZnZrO<sub><em>x</em></sub>/ZSM-5 catalysts have abundant oxygen vacancies which are active for the transformation CO<sub>2</sub> to aromatics; under 275 °C, H<sub>2</sub>/CO<sub>2</sub> = 3, and a space velocity of 600 mL/(g·h), the Fe(4)-ZnZrO<sub><em>x</em></sub>/ZSM-5 catalyst with an Fe mass fraction of 4% achieves a selectivity of 80.4% to aromatics, where tetramethylbenzene accounts for more than 70.4%, with a single-pass CO<sub>2</sub> conversion of 5.6%. A further increase of the Fe content to 8% can even improve the selectivity to aromatics (85.0%). Such observation should be useful for the design of industrial catalysts efficient for the direct conversion of CO<sub>2</sub> to aromatics.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 7","pages":"Pages 1038-1049"},"PeriodicalIF":0.0,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144696846","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-01DOI: 10.1016/S1872-5813(24)60527-X
Yan ZHAO , Xiang LI , Huanran WANG , Yaming ZHU , Xianchun LI
The microscopic reaction mechanism of NO reduction by CO on the graphene-supported single-atom Ni catalyst (Ni/G) was investigated by using density functional theory (DFT) and microkinetic modeling. The results indicate that as the most probably pathway for the NO reduction by CO over the Ni/G catalyst, two NO molecules adsorb onto the Ni atoms via the Langmuir-Hinshelwood mechanism and then transform to N2O and active oxygen (O*). Subsequently, N2O is adsorbed on the Ni surface and reduced to N2 and O*. Finally, CO reduces O* to form CO2, releasing the active Ni sites. From the energy barrier perspective, the transformation of NO to N2O and O* has a higher energy barrier, which controls the NO reduction reaction rate. From the microkinetic perspective, the reaction temperature has a significant effect on the rate of O* reduction with CO, which is lower than that of N2O reduction. As a result, the Ni atoms are gradually occupied by O*, which may inhibit the adsorption and reduction of NO, leading to the deactivation of the Ni/G catalyst.
{"title":"Mechanism of NO reduction by CO over single atomic nickel catalyst: DFT and microkinetic study","authors":"Yan ZHAO , Xiang LI , Huanran WANG , Yaming ZHU , Xianchun LI","doi":"10.1016/S1872-5813(24)60527-X","DOIUrl":"10.1016/S1872-5813(24)60527-X","url":null,"abstract":"<div><div>The microscopic reaction mechanism of NO reduction by CO on the graphene-supported single-atom Ni catalyst (Ni/G) was investigated by using density functional theory (DFT) and microkinetic modeling. The results indicate that as the most probably pathway for the NO reduction by CO over the Ni/G catalyst, two NO molecules adsorb onto the Ni atoms via the Langmuir-Hinshelwood mechanism and then transform to N<sub>2</sub>O and active oxygen (O*). Subsequently, N<sub>2</sub>O is adsorbed on the Ni surface and reduced to N<sub>2</sub> and O*. Finally, CO reduces O* to form CO<sub>2</sub>, releasing the active Ni sites. From the energy barrier perspective, the transformation of NO to N<sub>2</sub>O and O* has a higher energy barrier, which controls the NO reduction reaction rate. From the microkinetic perspective, the reaction temperature has a significant effect on the rate of O* reduction with CO, which is lower than that of N<sub>2</sub>O reduction. As a result, the Ni atoms are gradually occupied by O*, which may inhibit the adsorption and reduction of NO, leading to the deactivation of the Ni/G catalyst.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 7","pages":"Pages 1061-1071"},"PeriodicalIF":0.0,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144696625","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-01DOI: 10.1016/S1872-5813(25)60536-6
Liang ZHANG , Yajiao LI , Na WANG , Huidong XIE , Kaiyue YANG , Chang YANG , Chengmin GE
Cu-Ce catalysts have been extensively studied owing to their excellent low-temperature CO oxidation activity. However, they are prone to deactivation in the presence of both water vapor and sulfur. In this study, Ce-Cu-Sm CO oxidation catalysts with enhanced sulfur resistance were synthesized by Sm doping using three methods: combustion, co-precipitation, and acid solution synergistic co-precipitation. The mechanism underlying the improved sulfur resistance was investigated using XRD, TEM, N₂ adsorption and desorption, XPS, H2-TPR, and CO-TPD techniques. The results revealed that, under the coexistence of 1% CO, 10% H2O, and 0.01% SO2, the 20Ce-5Cu-4Sm-CG catalyst (prepared via acid solution synergistic co-precipitation) maintained a 100% CO oxidation efficiency for 220 min at 220 °C and a space velocity of 60000 mL/(g·h). After 280 min, the performance of the 20Ce-5Cu-4Sm-CG catalyst decreased to 70%, which was 1.3 times and 2.5 times higher than that of the 20Ce-5Cu-4Sm-C and 20Ce-5Cu-C catalysts prepared by the co-precipitation method, respectively. Characterization analysis revealed that Sm doping increased the CeO2 crystal size to a certain extent and reduced the specific surface area of the catalyst. However, it also enhanced the concentrations of Ce3+, Cu⁺, and surface oxygen atoms, as well as the ratio of Oα and the number of oxygen vacancies in the CeO2 lattice, which collectively improved the ability of the catalyst to oxidize CO under sulfur-containing atmosphere. The acid solution combustion synergistic co-precipitation method not only enhanced these five key properties for CO oxidation mentioned above, but also facilitated the formation of coordination complexes with the acid solution and Sm ions during combustion. These complexes were incorporated into the CeO2 lattice to form a homogeneous solid solution, which made the catalyst particle size more uniform and the specific surface area larger, and eliminated the adverse effects of Sm doping on the surface structure. As a result, the oxidation ability of the catalyst was further improved. In summary, the 20Ce-5Cu-4Sm catalyst, prepared via the acid solution combustion and co-precipitation method, exhibits excellent sulfur resistance and enhances the performance of non-precious metal oxide CO oxidation catalysts for applications in sulfur-containing environments.
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Lignin is recognized as the most abundant renewable aromatic polymer in nature with the highest concentration of benzene ring structures, and it stands out for its eco-friendly, sustainable, and biodegradable properties. The valorization of lignin through biorefinery strategies to produce aromatic compounds, which are subsequently converted into tailored lignin-derived liquid fuels via catalytic hydrogenation, deoxygenation, and other upgrading processes, has become a central focus in comprehensive biomass utilization research. This article systematically reviews the fundamental aspects and technological advancements in lignin-to-fuel conversion. Initially, it elaborates on the basic structural units of lignin—primarily the three phenylpropane monomers (guaiacyl, syringyl, and p-hydroxyphenyl units)—and their diverse interunit linkages, including β-O-4, α-O-4, 4-O-5, β-β, β-5, and 5-5 bonds, which collectively contribute to lignin's structural complexity and recalcitrance. These linkages dictate the depolymerization challenges and influence the selection of conversion pathways. Subsequently, it comprehensively reviews the principal technical pathways for manufacturing bio-based liquid fuels from lignin, particularly detailing three strategic approaches for producing liquid-phase products: lignin gasification-Fischer-Tropsch synthesis by gasifying lignin into syngas (CO/H2) and then catalytically reassembling into liquid hydrocarbons, lignin pyrolysis liquefaction involving thermal decomposition at 400–800 °C under inert conditions to yield bio-oil, and lignin liquid-phase catalytic conversion by employing solvents and catalysts to depolymerize lignin into monomers under milder conditions. Special emphasis is placed on analyzing key technologies in fuel production, including catalytic hydrodeoxygenation (HDO) and carbon-carbon coupling reactions. The discussion critically evaluates current technological limitations and challenges in lignin-to-fuel conversion, highlighting two pivotal technical bottlenecks requiring urgent resolution: the design and optimization of more stable and efficient catalytic systems, and the improvement of separation/purification processes for lignin depolymerization products. Furthermore, building upon contemporary research trends in bio-liquid fuels, the paper proposes that future investigations should prioritize the development of high-carbon-number cyclic aviation biofuels and high-density biodiesel derived from lignin. These directions are particularly promising given lignin's unique aromatic structure and high energy density characteristics, which align well with the stringent performance requirements of advanced transportation fuels. The analysis underscores the necessity for interdisciplinary collaboration between catalysis science, process engineering, and materials chemistry to overcome existing barriers. Specifically, the development of multifunctional catalysts capable of simultaneously act
木质素是自然界中含量最多、苯环结构含量最高的可再生芳香族聚合物，具有环保、可持续、可生物降解等特点。通过生物精炼策略使木质素增值以生产芳香族化合物，这些化合物随后通过催化加氢、脱氧和其他升级过程转化为定制的木质素衍生液体燃料，已成为生物质综合利用研究的中心焦点。本文系统地综述了木质素转化为燃料的基本方面和技术进展。首先，它详细阐述了木质素的基本结构单元-主要是三个苯丙烷单体（愈创木酰基、丁香基和对羟基苯基）-以及它们不同的单元间键，包括β- o -4、α-O-4、4-O-5、β-β、β-5和5-5键，这些键共同促进了木质素的结构复杂性和顽固性。这些联系决定了解聚的挑战并影响了转化途径的选择。随后，它全面回顾了从木质素生产生物基液体燃料的主要技术途径，特别是详细介绍了生产液相产品的三种战略方法：木质素气化-费托合成：木质素气化成合成气（CO/H2），然后催化重组成液态烃；木质素热解液化：在惰性条件下400-800℃热分解，生成生物油；木质素液相催化转化：在温和条件下，溶剂和催化剂将木质素解聚成单体。特别强调分析燃料生产中的关键技术，包括催化加氢脱氧（HDO）和碳-碳偶联反应。讨论批判性地评估了当前木质素到燃料转化的技术限制和挑战，强调了两个迫切需要解决的关键技术瓶颈：设计和优化更稳定和高效的催化系统，以及改进木质素解聚产物的分离/纯化过程。此外，基于当前生物液体燃料的研究趋势，本文提出未来的研究应优先发展高碳数循环航空生物燃料和木质素衍生的高密度生物柴油。鉴于木质素独特的芳香结构和高能量密度特性，这些方向特别有前景，这与先进运输燃料的严格性能要求非常一致。分析强调了催化科学、工艺工程和材料化学之间跨学科合作的必要性，以克服现有的障碍。具体来说，开发能够同时激活多种反应途径，同时在恶劣加工条件下抵抗失活的多功能催化剂是一个关键的研究前沿。此外，膜过滤和离子液体萃取等新型分离技术与传统蒸馏方法的结合可能会彻底改变复杂木质素衍生混合物的纯化。从工业应用的角度出发，本文强调了建立技术经济模型和生命周期评估的重要性，以评估各种木质素转化途径的商业可行性和环境效益。还讨论了木质素增值与现有石油精炼基础设施之间的潜在协同作用，作为加速技术部署的战略途径。总之，虽然在了解木质素转化机制方面取得了重大进展，但从实验室规模的成果到工业实施的转变需要在催化剂创新、工艺强化和系统集成方面持续努力。实现具有经济竞争力的木质素衍生液体燃料可以从根本上改变可再生能源格局，为化石运输燃料提供可持续的替代品，同时充分利用木质纤维素生物质资源。
{"title":"Research progress in catalytic conversion of lignin to produce liquid fuels","authors":"Yixiang WU , Ying XU , Xu ZENG , Liming LU , Jianchun JIANG","doi":"10.1016/S1872-5813(25)60539-1","DOIUrl":"10.1016/S1872-5813(25)60539-1","url":null,"abstract":"<div><div>Lignin is recognized as the most abundant renewable aromatic polymer in nature with the highest concentration of benzene ring structures, and it stands out for its eco-friendly, sustainable, and biodegradable properties. The valorization of lignin through biorefinery strategies to produce aromatic compounds, which are subsequently converted into tailored lignin-derived liquid fuels via catalytic hydrogenation, deoxygenation, and other upgrading processes, has become a central focus in comprehensive biomass utilization research. This article systematically reviews the fundamental aspects and technological advancements in lignin-to-fuel conversion. Initially, it elaborates on the basic structural units of lignin—primarily the three phenylpropane monomers (guaiacyl, syringyl, and p-hydroxyphenyl units)—and their diverse interunit linkages, including β-O-4, α-O-4, 4-O-5, β-β, β-5, and 5-5 bonds, which collectively contribute to lignin's structural complexity and recalcitrance. These linkages dictate the depolymerization challenges and influence the selection of conversion pathways. Subsequently, it comprehensively reviews the principal technical pathways for manufacturing bio-based liquid fuels from lignin, particularly detailing three strategic approaches for producing liquid-phase products: lignin gasification-Fischer-Tropsch synthesis by gasifying lignin into syngas (CO/H<sub>2</sub>) and then catalytically reassembling into liquid hydrocarbons, lignin pyrolysis liquefaction involving thermal decomposition at 400–800 °C under inert conditions to yield bio-oil, and lignin liquid-phase catalytic conversion by employing solvents and catalysts to depolymerize lignin into monomers under milder conditions. Special emphasis is placed on analyzing key technologies in fuel production, including catalytic hydrodeoxygenation (HDO) and carbon-carbon coupling reactions. The discussion critically evaluates current technological limitations and challenges in lignin-to-fuel conversion, highlighting two pivotal technical bottlenecks requiring urgent resolution: the design and optimization of more stable and efficient catalytic systems, and the improvement of separation/purification processes for lignin depolymerization products. Furthermore, building upon contemporary research trends in bio-liquid fuels, the paper proposes that future investigations should prioritize the development of high-carbon-number cyclic aviation biofuels and high-density biodiesel derived from lignin. These directions are particularly promising given lignin's unique aromatic structure and high energy density characteristics, which align well with the stringent performance requirements of advanced transportation fuels. The analysis underscores the necessity for interdisciplinary collaboration between catalysis science, process engineering, and materials chemistry to overcome existing barriers. Specifically, the development of multifunctional catalysts capable of simultaneously act","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"53 7","pages":"Pages 994-1008"},"PeriodicalIF":0.0,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144696897","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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