The concentration of carbon dioxide (CO2) in the atmosphere has been progressively increasing, resulting in the deterioration of the human living environment. Converting CO2 into valuable chemical products represents one of the most promising solutions to mitigate these environmental challenges. Among various approaches, the production of methanol from CO2 and H2 via photothermal catalysis stands out as an important way for CO2 resource utilization. Photothermal catalysis combines the advantages of both photocatalysis and thermal catalysis, thereby enhancing CO2 conversion efficiency and methanol selectivity. In this study, the catalysts Ru-In2O3 and Ru-In2O3/g-C3N4 for converting CO2 into methanol were prepared by coprecipitation method. More oxygen vacancies were created in In2O3 and band gap was narrowed after doping ruthenium. More active sites and better charge separation capability were provided by the addition of g-C3N4. When Ru-In2O3/1.5 % g-C3N4 was used as the catalyst, the methanol space–time yield was up to 114.68 gMeOH·h−1·kgcat-1, and the catalytic performance tested under photothermal reaction conditions at 265 ℃ and 1.0 MPa remained stable in 20 h. This work provides a new strategy for promoting the development of CO2 hydrogenation to methanol under conditions of low temperature and low pressure.
{"title":"Ru-In2O3/g-C3N4 photothermal coupling catalyzed boosted carbon dioxide hydrogenation to methanol","authors":"Qi Zhang, Guolin Zhang, Liangyun Yu, Hui Huang, Ying Zhang, Yanbo Zhang, Yongxin Wang, Fang Guo, Qi Xu","doi":"10.1016/j.apsusc.2025.162872","DOIUrl":"https://doi.org/10.1016/j.apsusc.2025.162872","url":null,"abstract":"The concentration of carbon dioxide (CO<sub>2</sub>) in the atmosphere has been progressively increasing, resulting in the deterioration of the human living environment. Converting CO<sub>2</sub> into valuable chemical products represents one of the most promising solutions to mitigate these environmental challenges. Among various approaches, the production of methanol from CO<sub>2</sub> and H<sub>2</sub> via photothermal catalysis stands out as an important way for CO<sub>2</sub> resource utilization. Photothermal catalysis combines the advantages of both photocatalysis and thermal catalysis, thereby enhancing CO<sub>2</sub> conversion efficiency and methanol selectivity. In this study, the catalysts Ru-In<sub>2</sub>O<sub>3</sub> and Ru-In<sub>2</sub>O<sub>3</sub>/g-C<sub>3</sub>N<sub>4</sub> for converting CO<sub>2</sub> into methanol were prepared by coprecipitation method. More oxygen vacancies were created in In<sub>2</sub>O<sub>3</sub> and band gap was narrowed after doping ruthenium. More active sites and better charge separation capability were provided by the addition of g-C<sub>3</sub>N<sub>4</sub>. When Ru-In<sub>2</sub>O<sub>3</sub>/1.5 % g-C<sub>3</sub>N<sub>4</sub> was used as the catalyst, the methanol space–time yield was up to 114.68 g<sub>MeOH</sub>·h<sup>−1</sup>·kg<sub>cat</sub><sup>-1</sup>, and the catalytic performance tested under photothermal reaction conditions at 265 ℃ and 1.0 MPa remained stable in 20 h. This work provides a new strategy for promoting the development of CO<sub>2</sub> hydrogenation to methanol under conditions of low temperature and low pressure.","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"23 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539041","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","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.apsusc.2025.162868
XianFeng Zhao, ChangChun Ge
In this paper, a novel two-step reductive molecular blending strategy was proposed, in which Ag atoms were preferentially coated on the surface of carbon nanotubes (CNTs) to prepare composite metal powders with evenly distributed CNTs. Whereafter, the CNTs reinforced CuAg alloy matrix composites (CNTs-CuAg) were produced through hot pressing sintering process. The composite powders after corrosion treatment were characterized by scanning electron microscopy (SEM). The results demonstrated that the Ag and Cu atoms coated on the CNTs effectively prevented the agglomeration of CNTs in the matrix through the novel two-step reduction molecular-level blending method. Through the mechanical properties test, the tensile strength of CNTs-CuAg composites significantly increased, reaching 269 MPa (26.3 % higher than that of pure Cu). It is exciting that the results of the conductivity test showed the CNTs-CuAg composites obtain excellent electrical conductivity (94 % IACS) compared with CuAg alloy and CNTs/Cu composite. Meanwhile, the reinforcement mechanism, fracture mode and the reason for the high electrical conductivity of the CNTs-CuAg composites were discussed. Furthermore, the work in this paper can provide an effective way for designing and manufacturing advanced Cu alloy matrix composites with excellent strength and electrical conductivity.
{"title":"Synchronously enhance the mechanical properties and electrical conductivity of CNTs-CuAg composites via two-step reduction molecular-level blending","authors":"XianFeng Zhao, ChangChun Ge","doi":"10.1016/j.apsusc.2025.162868","DOIUrl":"https://doi.org/10.1016/j.apsusc.2025.162868","url":null,"abstract":"In this paper, a novel two-step reductive molecular blending strategy was proposed, in which Ag atoms were preferentially coated on the surface of carbon nanotubes (CNTs) to prepare composite metal powders with evenly distributed CNTs. Whereafter, the CNTs reinforced CuAg alloy matrix composites (CNTs-CuAg) were produced through hot pressing sintering process. The composite powders after corrosion treatment were characterized by scanning electron microscopy (SEM). The results demonstrated that the Ag and Cu atoms coated on the CNTs effectively prevented the agglomeration of CNTs in the matrix through the novel two-step reduction molecular-level blending method. Through the mechanical properties test, the tensile strength of CNTs-CuAg composites significantly increased, reaching 269 MPa (26.3 % higher than that of pure Cu). It is exciting that the results of the conductivity test showed the CNTs-CuAg composites obtain excellent electrical conductivity (94 % IACS) compared with CuAg alloy and CNTs/Cu composite. Meanwhile, the reinforcement mechanism, fracture mode and the reason for the high electrical conductivity of the CNTs-CuAg composites were discussed. Furthermore, the work in this paper can provide an effective way for designing and manufacturing advanced Cu alloy matrix composites with excellent strength and electrical conductivity.","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"30 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143546494","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Single atom metal-nitrogen-carbon catalysts (MN4C) distributed on carbon materials demonstrate excellent performance in oxygen reduction/evolution reaction (ORR/OER) oxygen electrocatalytic processes. In this study, interlayer covalent interaction of graphene on the ORR/OER performance of CoN4 is investigated based on first-principles calculations. It is revealed that interlayer covalent interaction results in CoN4 distortions, which can alter the adsorption strength of reaction intermediates at active sites. CoN4 with the best ORR/OER performance is determined, and the overpotentials are consistent with the reported experimental results. Thereby, the volcanic relationship between the distortion of CoN4 and ORR/OER overpotential is determined. Electronic structure analysis shows that distortions caused by interlayer covalent interactions and vacancy defects lead to the differentiation of Co 3d orbitals and the upshift of Co 4s orbitals, resulting in an optimized covalent composition of CoO bonds and ultimately optimizing the binding strength of intermediates. The results provide an in-depth understanding of the structure–activity relationship on MN4C, and are helpful for the design of single atom catalysts.
{"title":"Enhanced ORR and OER bifunctional performance of Co-N-C single atom catalyst by interlayer covalent interaction of graphene","authors":"Depeng Meng, Hongpeng Chen, Jinshuo Pang, Chunnian He, Chunsheng Shi, Naiqin Zhao, Enzuo Liu","doi":"10.1016/j.apsusc.2025.162879","DOIUrl":"https://doi.org/10.1016/j.apsusc.2025.162879","url":null,"abstract":"Single atom metal-nitrogen-carbon catalysts (MN<sub>4</sub>C) distributed on carbon materials demonstrate excellent performance in oxygen reduction/evolution reaction (ORR/OER) oxygen electrocatalytic processes. In this study, interlayer covalent interaction of graphene on the ORR/OER performance of CoN<sub>4</sub> is investigated based on first-principles calculations. It is revealed that interlayer covalent interaction results in CoN<sub>4</sub> distortions, which can alter the adsorption strength of reaction intermediates at active sites. CoN<sub>4</sub> with the best ORR/OER performance is determined, and the overpotentials are consistent with the reported experimental results. Thereby, the volcanic relationship between the distortion of CoN<sub>4</sub> and ORR/OER overpotential is determined. Electronic structure analysis shows that distortions caused by interlayer covalent interactions and vacancy defects lead to the differentiation of Co 3d orbitals and the upshift of Co 4s orbitals, resulting in an optimized covalent composition of Co<img alt=\"single bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/sbnd.gif\" style=\"vertical-align:middle\"/>O bonds and ultimately optimizing the binding strength of intermediates. The results provide an in-depth understanding of the structure–activity relationship on MN<sub>4</sub>C, and are helpful for the design of single atom catalysts.","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"6 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143546496","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mo2C is considered to be an ideal material to replace Pt in electrocatalytic hydrogen evolution reaction (HER), but the strong hydrogen adsorption by Mo atoms in Mo2C leads to difficulties in hydrogen desorption, limiting its wide application. In this work, independently dispersed bilayered hollow nanocore-shell spherical molybdenum carbide/carbon heterostructure (Mo2C/C) electrocatalytic materials were constructed through a facile method. The unique double-layer hollow nanosphere structure of Mo2C/C has great specific surface area (SSA) and porosity, making the catalytic active sites exposed on the material surface to a larger extent and accelerating the charge transport of its HER process. Moreover, it generates more defects at the interface of Mo2C/C heterostructure and makes Mo2C have a lower d-band center, which greatly weakens the bonding strength of Mo–H*, thus optimizing the free energy of hydrogen adsorption by Mo2C and improving the hydrogen evolution efficiency. This is shown by the η10 (overpotential at 10 mA·cm−2) and Tafel slopes of 132 mV, 185 mV and 88 mV·dec−1, 84 mV·dec−1 for Mo2C/C in 1 M KOH and 0.5 M H2SO4, respectively. The present work guides the development of structurally controllable and stable and efficient HER electrocatalysts.
{"title":"Highly efficient electrocatalytic hydrogen evolution by double-shelled hollow spheres with Mo2C/C heterostructure","authors":"Xin Chen, Hongyu Liu, Aihua Jiang, Xinyu Li, Jianrong Xiao","doi":"10.1016/j.apsusc.2025.162869","DOIUrl":"10.1016/j.apsusc.2025.162869","url":null,"abstract":"<div><div>Mo<sub>2</sub>C is considered to be an ideal material to replace Pt in electrocatalytic hydrogen evolution reaction (HER), but the strong hydrogen adsorption by Mo atoms in Mo<sub>2</sub>C leads to difficulties in hydrogen desorption, limiting its wide application. In this work, independently dispersed bilayered hollow nanocore-shell spherical molybdenum carbide/carbon heterostructure (Mo<sub>2</sub>C/C) electrocatalytic materials were constructed through a facile method. The unique double-layer hollow nanosphere structure of Mo<sub>2</sub>C/C has great specific surface area (SSA) and porosity, making the catalytic active sites exposed on the material surface to a larger extent and accelerating the charge transport of its HER process. Moreover, it generates more defects at the interface of Mo<sub>2</sub>C/C heterostructure and makes Mo<sub>2</sub>C have a lower d-band center, which greatly weakens the bonding strength of Mo–H*, thus optimizing the free energy of hydrogen adsorption by Mo<sub>2</sub>C and improving the hydrogen evolution efficiency. This is shown by the η<sub>10</sub> (overpotential at 10 mA·cm<sup>−2</sup>) and Tafel slopes of 132 mV, 185 mV and 88 mV·dec<sup>−1</sup>, 84 mV·dec<sup>−1</sup> for Mo<sub>2</sub>C/C in 1 M KOH and 0.5 M H<sub>2</sub>SO<sub>4</sub>, respectively. The present work guides the development of structurally controllable and stable and efficient HER electrocatalysts.</div></div>","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"695 ","pages":"Article 162869"},"PeriodicalIF":6.3,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539040","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","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.apsusc.2025.162790
Mikko Miettinen, Esa Vuorinen, Juha-Pekka Lehtiö, Zahra Jahanshah Rad, Risto Punkkinen, Mikhail Kuzmin, Jarno Järvinen, Ville Vähänissi, Pekka Laukkanen, Hele Savin, Kalevi Kokko
Most electronic and photonic devices include ohmic metal–semiconductor junction(s), of which contact resistivity needs to be minimized for best efficiency of the devices. Interface defects in the junction usually degrade the junction’s performance, thus cleaning and passivation of semiconductor surface is crucial during contact fabrication. For silicon devices the RCA (Radio Corporation of America) cleaning has been the most known method. Here we have addressed the question whether it is still possible to develop Si surface treatments to decrease the contact resistivity. We have combined wet chemistry and ultra-high vacuum (UHV) heating for two cases: low and highly phosphorus-doped n-type Si. As compared to silicon surfaces treated only with wet chemistry, the contact resistivity is lowered when (i) lowly doped n-Si is rapidly heated at temperature around 1200 <span><span style=""></span><span data-mathml='<math xmlns="http://www.w3.org/1998/Math/MathML"><mrow is="true"><mo is="true">°</mo><mi mathvariant="normal" is="true">C</mi></mrow></math>' role="presentation" style="font-size: 90%; display: inline-block; position: relative;" tabindex="0"><svg aria-hidden="true" focusable="false" height="2.086ex" role="img" style="vertical-align: -0.235ex;" viewbox="0 -796.9 1223 898.2" width="2.841ex" xmlns:xlink="http://www.w3.org/1999/xlink"><g fill="currentColor" stroke="currentColor" stroke-width="0" transform="matrix(1 0 0 -1 0 0)"><g is="true"><g is="true"><use xlink:href="#MJMAIN-B0"></use></g><g is="true" transform="translate(500,0)"><use xlink:href="#MJMAIN-43"></use></g></g></g></svg><span role="presentation"><math xmlns="http://www.w3.org/1998/Math/MathML"><mrow is="true"><mo is="true">°</mo><mi is="true" mathvariant="normal">C</mi></mrow></math></span></span><script type="math/mml"><math><mrow is="true"><mo is="true">°</mo><mi mathvariant="normal" is="true">C</mi></mrow></math></script></span> in UHV followed by hydrofluoric (HF) acid dip before Ni sputtering; (ii) p-Si substrate with highly n-type surface is first immersed in HF, then UHV heated at 400 <span><span style=""></span><span data-mathml='<math xmlns="http://www.w3.org/1998/Math/MathML"><mrow is="true"><mo is="true">°</mo><mi mathvariant="normal" is="true">C</mi></mrow></math>' role="presentation" style="font-size: 90%; display: inline-block; position: relative;" tabindex="0"><svg aria-hidden="true" focusable="false" height="2.086ex" role="img" style="vertical-align: -0.235ex;" viewbox="0 -796.9 1223 898.2" width="2.841ex" xmlns:xlink="http://www.w3.org/1999/xlink"><g fill="currentColor" stroke="currentColor" stroke-width="0" transform="matrix(1 0 0 -1 0 0)"><g is="true"><g is="true"><use xlink:href="#MJMAIN-B0"></use></g><g is="true" transform="translate(500,0)"><use xlink:href="#MJMAIN-43"></use></g></g></g></svg><span role="presentation"><math xmlns="http://www.w3.org/
{"title":"Effects of ultra-high vacuum treatments on n-type Si contact resistivity","authors":"Mikko Miettinen, Esa Vuorinen, Juha-Pekka Lehtiö, Zahra Jahanshah Rad, Risto Punkkinen, Mikhail Kuzmin, Jarno Järvinen, Ville Vähänissi, Pekka Laukkanen, Hele Savin, Kalevi Kokko","doi":"10.1016/j.apsusc.2025.162790","DOIUrl":"https://doi.org/10.1016/j.apsusc.2025.162790","url":null,"abstract":"Most electronic and photonic devices include ohmic metal–semiconductor junction(s), of which contact resistivity needs to be minimized for best efficiency of the devices. Interface defects in the junction usually degrade the junction’s performance, thus cleaning and passivation of semiconductor surface is crucial during contact fabrication. For silicon devices the RCA (Radio Corporation of America) cleaning has been the most known method. Here we have addressed the question whether it is still possible to develop Si surface treatments to decrease the contact resistivity. We have combined wet chemistry and ultra-high vacuum (UHV) heating for two cases: low and highly phosphorus-doped n-type Si. As compared to silicon surfaces treated only with wet chemistry, the contact resistivity is lowered when (i) lowly doped n-Si is rapidly heated at temperature around 1200 <span><span style=\"\"></span><span data-mathml='<math xmlns=\"http://www.w3.org/1998/Math/MathML\"><mrow is=\"true\"><mo is=\"true\">&#xB0;</mo><mi mathvariant=\"normal\" is=\"true\">C</mi></mrow></math>' role=\"presentation\" style=\"font-size: 90%; display: inline-block; position: relative;\" tabindex=\"0\"><svg aria-hidden=\"true\" focusable=\"false\" height=\"2.086ex\" role=\"img\" style=\"vertical-align: -0.235ex;\" viewbox=\"0 -796.9 1223 898.2\" width=\"2.841ex\" xmlns:xlink=\"http://www.w3.org/1999/xlink\"><g fill=\"currentColor\" stroke=\"currentColor\" stroke-width=\"0\" transform=\"matrix(1 0 0 -1 0 0)\"><g is=\"true\"><g is=\"true\"><use xlink:href=\"#MJMAIN-B0\"></use></g><g is=\"true\" transform=\"translate(500,0)\"><use xlink:href=\"#MJMAIN-43\"></use></g></g></g></svg><span role=\"presentation\"><math xmlns=\"http://www.w3.org/1998/Math/MathML\"><mrow is=\"true\"><mo is=\"true\">°</mo><mi is=\"true\" mathvariant=\"normal\">C</mi></mrow></math></span></span><script type=\"math/mml\"><math><mrow is=\"true\"><mo is=\"true\">°</mo><mi mathvariant=\"normal\" is=\"true\">C</mi></mrow></math></script></span> in UHV followed by hydrofluoric (HF) acid dip before Ni sputtering; (ii) p-Si substrate with highly n-type surface is first immersed in HF, then UHV heated at 400 <span><span style=\"\"></span><span data-mathml='<math xmlns=\"http://www.w3.org/1998/Math/MathML\"><mrow is=\"true\"><mo is=\"true\">&#xB0;</mo><mi mathvariant=\"normal\" is=\"true\">C</mi></mrow></math>' role=\"presentation\" style=\"font-size: 90%; display: inline-block; position: relative;\" tabindex=\"0\"><svg aria-hidden=\"true\" focusable=\"false\" height=\"2.086ex\" role=\"img\" style=\"vertical-align: -0.235ex;\" viewbox=\"0 -796.9 1223 898.2\" width=\"2.841ex\" xmlns:xlink=\"http://www.w3.org/1999/xlink\"><g fill=\"currentColor\" stroke=\"currentColor\" stroke-width=\"0\" transform=\"matrix(1 0 0 -1 0 0)\"><g is=\"true\"><g is=\"true\"><use xlink:href=\"#MJMAIN-B0\"></use></g><g is=\"true\" transform=\"translate(500,0)\"><use xlink:href=\"#MJMAIN-43\"></use></g></g></g></svg><span role=\"presentation\"><math xmlns=\"http://www.w3.org/","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"2 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539216","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","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.apsusc.2025.162864
Danilo A. Nagaoka, Leandro Hostert, Rogério Gelamo, Camila M. Maroneze, Denise Maria de Andrade, Alisson R. Cadore, Christiano J.S. de Matos
Niobium disulfide (NbS2) is a layered transition metal dichalcogenide (TMD) with metallic characteristics. While mono- and few-layer NbS2 have been explored by various research groups, significant challenges remain in achieving continuous films. In this study, we present a procedure for converting centimeter-scale thin films of niobium oxide (NbxOy), deposited using physical vapor deposition (PVD), into a continuous, crystalline, mixed-phase (2H/3R) NbS2 film through sulfurization. We examine the influence of the initial NbxOy film thickness on the NbS2 conversion and stability. Adjusting the initial NbxOy thickness results in distinct roughness profiles, electrical resistivities and stabilities against re-oxidation. The NbS2 films demonstrate intrinsically low resistivity, measuring at 190 ± 23 Ω/sqr (80 ± 5 Ω/sqr) for the thinner (thicker) film. However, over a 21-day exposure to air, the long-term stability of these films varies with thickness. Thinner films show a significant increase in resistivity, rising by 367 % to 699 ± 97 Ω/sqr. In contrast, the thicker film exhibits a modest increase of only 22 %, reaching 97 ± 5 Ω/sqr. Even after one year of air exposure, the thicker film remains conductive, and the initial characteristics of the converted films can be restored through the resulfurization process. This process enables the scalable production of large-area NbS2 films, suitable for nanotechnological applications.
{"title":"Conversion of centimeter-scale amorphous niobium oxide thin films into crystalline niobium disulfide (NbS2): Synthesis and stability","authors":"Danilo A. Nagaoka, Leandro Hostert, Rogério Gelamo, Camila M. Maroneze, Denise Maria de Andrade, Alisson R. Cadore, Christiano J.S. de Matos","doi":"10.1016/j.apsusc.2025.162864","DOIUrl":"https://doi.org/10.1016/j.apsusc.2025.162864","url":null,"abstract":"Niobium disulfide (NbS<sub>2</sub>) is a layered transition metal dichalcogenide (TMD) with metallic characteristics. While mono- and few-layer NbS<sub>2</sub> <!-- -->have been explored by various research groups, significant challenges remain in achieving continuous films. In this study, we present a procedure for converting centimeter-scale thin films of niobium oxide (Nb<sub>x</sub>O<sub>y</sub>), deposited using physical vapor deposition (PVD), into a continuous, crystalline, mixed-phase (2H/3R) NbS<sub>2</sub> <!-- -->film through sulfurization. We examine the influence of the initial Nb<sub>x</sub>O<sub>y</sub> <!-- -->film thickness on the NbS<sub>2</sub> <!-- -->conversion and stability. Adjusting the initial Nb<sub>x</sub>O<sub>y</sub> <!-- -->thickness results in distinct roughness profiles, electrical resistivities and stabilities against re-oxidation. The NbS<sub>2</sub> <!-- -->films demonstrate intrinsically low resistivity, measuring at 190 ± 23 Ω/sqr (80 ± 5 Ω/sqr) for the thinner (thicker) film. However, over a 21-day exposure to air, the long-term stability of these films varies with thickness. Thinner films show a significant increase in resistivity, rising by 367 % to 699 ± 97 Ω/sqr. In contrast, the thicker film exhibits a modest increase of only 22 %, reaching 97 ± 5 Ω/sqr. Even after one year of air exposure, the thicker film remains conductive, and the initial characteristics of the converted films can be restored through the resulfurization process. This process enables the scalable production of large-area NbS<sub>2</sub> <!-- -->films, suitable for nanotechnological applications.","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"74 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143546448","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","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.apsusc.2025.162865
Yuanyuan Sun , Wen Zhao , Wei Cai , Yuhua Chi , Hao Ren , Zhongtao Li
Electrocatalysis offers a promising approach for the oxidation of ethylene to high-value oxygenated products under ambient conditions, contributing to the balance between fossil energy consumption and environmental protection. However, the ethylene oxidation process requires conjunction with the oxygen evolution reaction (OER). In this study, first-principles calculations are employed to systematically investigate the catalytic performance of supported single-atom catalysts M/GDY for ethylene oxidation in OER-assisted. Our study focuses on using the adjustment of metal sites to influence the adsorption and activation of reaction intermediates, thereby regulating the reaction pathways and selectivity of final products in ethylene oxidation. The results show that Co, Cu, and Rh metal sites effectively stabilize the *OHCH2-CH2OH intermediate, promoting the formation of ethylene glycol oxidation products (HCOOH and OHCH2-COOH). Notably, the Rh/GDY catalyst exhibits excellent catalytic performance with a low voltage of 0.60 eV. Electronic structure analysis reveals that the interaction between the π electrons of ethylene and the metal atoms is crucial for ethylene activation. This study provides new insights into the mechanisms of ethylene oxidation and offers guidance for the development of efficient electrocatalysts.
{"title":"Single-atom M/GDY catalysts for electrochemical ethylene conversion via tandem water oxidation","authors":"Yuanyuan Sun , Wen Zhao , Wei Cai , Yuhua Chi , Hao Ren , Zhongtao Li","doi":"10.1016/j.apsusc.2025.162865","DOIUrl":"10.1016/j.apsusc.2025.162865","url":null,"abstract":"<div><div>Electrocatalysis offers a promising approach for the oxidation of ethylene to high-value oxygenated products under ambient conditions, contributing to the balance between fossil energy consumption and environmental protection. However, the ethylene oxidation process requires conjunction with the oxygen evolution reaction (OER). In this study, first-principles calculations are employed to systematically investigate the catalytic performance of supported single-atom catalysts M/GDY for ethylene oxidation in OER-assisted. Our study focuses on using the adjustment of metal sites to influence the adsorption and activation of reaction intermediates, thereby regulating the reaction pathways and selectivity of final products in ethylene oxidation. The results show that Co, Cu, and Rh metal sites effectively stabilize the *OHCH<sub>2</sub>-CH<sub>2</sub>OH intermediate, promoting the formation of ethylene glycol oxidation products (HCOOH and OHCH<sub>2</sub>-COOH). Notably, the Rh/GDY catalyst exhibits excellent catalytic performance with a low voltage of 0.60 eV. Electronic structure analysis reveals that the interaction between the π electrons of ethylene and the metal atoms is crucial for ethylene activation. This study provides new insights into the mechanisms of ethylene oxidation and offers guidance for the development of efficient electrocatalysts.</div></div>","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"695 ","pages":"Article 162865"},"PeriodicalIF":6.3,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539042","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","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.apsusc.2025.162886
Pei Song, Zhikai Gao, Tiren Peng, Zhiguo Wang, Sen Lu, Zepeng Jia, Zishan Luo, Hong Cui, Weizhi Tian, Rong Feng, Lingxia Jin, Hongkuan Yuan
Single-atom catalysts (SACs) have attracted much attention in the field of energy and environment due to their tunable activity. Here, we present a study of MXene(M2NO) carriers to modulate the catalytic activity and reactive metal dissolution of SAC at the M−N−C(MN4) interface. The density functional theory (DFT) results indicated that M2NO provides axial traction for MN4, weakening the interaction of M−3d orbitals with *O/*OH/*OOH-p orbitals in MN4, forming higher π* and π orbitals, and lowering the ORR or OER overpotential of FeN4/M2NO and CoN4/M2NO (Ti, V, Cr, Nb and Ta). Pourbaix diagrams were constructed based on thermodynamic cycling and DFT, and the results showed that FeN4/M2NO (M = Ti, V, Cr, Nb and Ta) had lower metal dissolution. And with the addition of 0.2 V/Ang interfacial electric field, FeN4/Ti2NO exhibits excellent OER (0.28 V) overpotential. The accuracy of the constructed simple descriptors of ORR and OER catalytic performance: EA1 × EA2-M1 and M1-a-b was demonstrated by four machine learning methods and symbolic regression algorithms. This study reveals the law of the influence of M2NO on the catalytic performance of the MN4 interface and improves new ideas for the design of high-performance SACs.
{"title":"Single-atom dissolution at the MN4/MXene interface and electric field-driven adsorption mechanisms: Unraveling catalytic descriptors using machine learning","authors":"Pei Song, Zhikai Gao, Tiren Peng, Zhiguo Wang, Sen Lu, Zepeng Jia, Zishan Luo, Hong Cui, Weizhi Tian, Rong Feng, Lingxia Jin, Hongkuan Yuan","doi":"10.1016/j.apsusc.2025.162886","DOIUrl":"https://doi.org/10.1016/j.apsusc.2025.162886","url":null,"abstract":"Single-atom catalysts (SACs) have attracted much attention in the field of energy and environment due to their tunable activity. Here, we present a study of MXene(M<sub>2</sub>NO) carriers to modulate the catalytic activity and reactive metal dissolution of SAC at the M−N−C(MN<sub>4</sub>) interface. The density functional theory (DFT) results indicated that M<sub>2</sub>NO provides axial traction for MN<sub>4</sub>, weakening the interaction of M−3<em>d</em> orbitals with *O/*OH/*OOH-<em>p</em> orbitals in MN<sub>4</sub>, forming higher π* and π orbitals, and lowering the ORR or OER overpotential of FeN<sub>4</sub>/M<sub>2</sub>NO and CoN<sub>4</sub>/M<sub>2</sub>NO (Ti, V, Cr, Nb and Ta). Pourbaix diagrams were constructed based on thermodynamic cycling and DFT, and the results showed that FeN<sub>4</sub>/M<sub>2</sub>NO (M = Ti, V, Cr, Nb and Ta) had lower metal dissolution. And with the addition of 0.2 V/Ang interfacial electric field, FeN<sub>4</sub>/Ti<sub>2</sub>NO exhibits excellent OER (0.28 V) overpotential. The accuracy of the constructed simple descriptors of ORR and OER catalytic performance: <em>EA</em><sub>1</sub> × <em>EA</em><sub>2</sub>-<em>M</em><sub>1</sub> and <em>M</em><sub>1</sub>-<em>a</em>-<em>b</em> was demonstrated by four machine learning methods and symbolic regression algorithms. This study reveals the law of the influence of M<sub>2</sub>NO on the catalytic performance of the MN<sub>4</sub> interface and improves new ideas for the design of high-performance SACs.","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"91 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143546449","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The effect of EDTA-2Na on the photocatalytic performance of bismuth-based compounds varied with their chemical compositions and EDTA dosage. For Bi2O3 and Bi5O7I with high Bi/anions ratios, coordinating with EDTA-2Na at molar ratios of 1.5:1 for Bi2O3 and 5:1 for Bi5O7I significantly improved photocatalytic activity of methyl violet (MV, 50 mg·L-1) degradation under visible irradiation, with apparent rate constants (k) of 0.0715 min−1 and 0.0261 min−1, which were 102 and 44 times of those for pure Bi2O3 and Bi5O7I, respectively. Besides, these samples also exhibited enhanced adsorption performance to cation dye MV due to decreased zero zeta potential. However, If the molar ratio of EDTA to Bi2O3 exceeded 4:1 and the molar ratio of EDTA to Bi5O7I exceeded 5:1, the samples possessed the poor photocatalytic performance for the degradation of MV, even inferior to pure Bi2O3 and Bi5O7I. Conversely, BiOX (X = Br, I) and Bi2O2CO3 with low Bi/anion ratios didn’t show significant improvement in photocatalytic activity, and BiVO4 and Bi2MoO6 with lower Bi/anion ratios exhibited even worse photocatalytic performance after coordinating with EDTA-2Na. Photocatalytic mechanism suggests that EDTA-2Na’s electron transfer capabilities to the conduction band of high Bi/anion ratio compounds promote reactive oxygen species generation, enhancing their photocatalytic performance. For the low Bi/anion ratio compounds, the electrons of EDTA would transit to VB and trap the holes, hindering the hole-dominant photo catalysis process.
{"title":"Tailoring photocatalytic performance through EDTA-2Na coordination: Competition of electron transfer to conduction band and valence band in bismuth-based compounds","authors":"Huiwei Ding, Zhihao Wang, Yu Guan, Rongyao Ma, Xin Tang, Qiaofeng Han","doi":"10.1016/j.apsusc.2025.162866","DOIUrl":"10.1016/j.apsusc.2025.162866","url":null,"abstract":"<div><div>The effect of EDTA-2Na on the photocatalytic performance of bismuth-based compounds varied with their chemical compositions and EDTA dosage. For Bi<sub>2</sub>O<sub>3</sub> and Bi<sub>5</sub>O<sub>7</sub>I with high Bi/anions ratios, coordinating with EDTA-2Na at molar ratios of 1.5:1 for Bi<sub>2</sub>O<sub>3</sub> and 5:1 for Bi<sub>5</sub>O<sub>7</sub>I significantly improved photocatalytic activity of methyl violet (MV, 50 mg·L<sup>-1</sup>) degradation under visible irradiation, with apparent rate constants (<em>k</em>) of 0.0715 min<sup>−1</sup> and 0.0261 min<sup>−1</sup>, which were 102 and 44 times of those for pure Bi<sub>2</sub>O<sub>3</sub> and Bi<sub>5</sub>O<sub>7</sub>I, respectively. Besides, these samples also exhibited enhanced adsorption performance to cation dye MV due to decreased zero zeta potential. However, If the molar ratio of EDTA to Bi<sub>2</sub>O<sub>3</sub> exceeded 4:1 and the molar ratio of EDTA to Bi<sub>5</sub>O<sub>7</sub>I exceeded 5:1, the samples possessed the poor photocatalytic performance for the degradation of MV, even inferior to pure Bi<sub>2</sub>O<sub>3</sub> and Bi<sub>5</sub>O<sub>7</sub>I. Conversely, BiOX (X = Br, I) and Bi<sub>2</sub>O<sub>2</sub>CO<sub>3</sub> with low Bi/anion ratios didn’t show significant improvement in photocatalytic activity, and BiVO<sub>4</sub> and Bi<sub>2</sub>MoO<sub>6</sub> with lower Bi/anion ratios exhibited even worse photocatalytic performance after coordinating with EDTA-2Na. Photocatalytic mechanism suggests that EDTA-2Na’s electron transfer capabilities to the conduction band of high Bi/anion ratio compounds promote reactive oxygen species generation, enhancing their photocatalytic performance. For the low Bi/anion ratio compounds, the electrons of EDTA would transit to VB and trap the holes, hindering the hole-dominant photo catalysis process.</div></div>","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"695 ","pages":"Article 162866"},"PeriodicalIF":6.3,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539043","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In industry, silver-based catalysts are the mainstream choice for converting ethylene to ethylene oxide (EO), and the morphology of Ag particles plays an important role in their catalytic performance; however, related studies are scarce. In this work, evidence from SEM shown that we successfully synthesized three different morphologies of Ag particles induced by different solvent, i.e., flower-like Ag (Fl-Ag), spheroidal Ag (Sp-Ag) and sheet-like Ag (Sh-Ag), dissolve them respectively into the mixed solution of silver nitrate/oxalic acid to form a suspension, then load onto α-Al2O3. Through were calculated from the XRD peak area the Ag(100) surface occupancy has the order of Fl-Ag (30 %) > Sh-Ag (20 %) > Sp-Ag (15 %), and the selectivity of EO has positive relation with similar order of Fl-Ag/Al2O3 (85 %) > Sh-Ag/ Al2O3 (72 %) > Sp-Ag/Al2O3 (70 %). The selectivity of Fl-Ag/Al2O3 for EO at 210 °C was 85 %. It is shown that Ag(100) surface has better O2 interaction and activated than that of Ag(111) surface, and (100) has a lower activation energy than the side reaction (0.9 eV vs 1.0 eV), facilitates the conversion of ethylene to ethylene oxide. This study provides a new method to design and optimize silver catalysts.
{"title":"Optimal morphologies of Ag particles on α-Al2O3 for ethylene epoxidation","authors":"Lijun Yang, Jiankun Liu, Yuxi Wang, Huanwen Zhou, Xiaoyuan Liao","doi":"10.1016/j.apsusc.2025.162863","DOIUrl":"https://doi.org/10.1016/j.apsusc.2025.162863","url":null,"abstract":"In industry, silver-based catalysts are the mainstream choice for converting ethylene to ethylene oxide (EO), and the morphology of Ag particles plays an important role in their catalytic performance; however, related studies are scarce. In this work, evidence from SEM shown that we successfully synthesized three different morphologies of Ag particles induced by different solvent, i.e., flower-like Ag (Fl-Ag), spheroidal Ag (Sp-Ag) and sheet-like Ag (Sh-Ag), dissolve them respectively into the mixed solution of silver nitrate/oxalic acid to form a suspension, then load onto α-Al<sub>2</sub>O<sub>3</sub>. Through were calculated from the XRD peak area the Ag(100) surface occupancy has the order of Fl-Ag (30 %) > Sh-Ag (20 %) > Sp-Ag (15 %), and the selectivity of EO has positive relation with similar order of Fl-Ag/Al<sub>2</sub>O<sub>3</sub> (85 %) > Sh-Ag/ Al<sub>2</sub>O<sub>3</sub> (72 %) > Sp-Ag/Al<sub>2</sub>O<sub>3</sub> (70 %). The selectivity of Fl-Ag/Al<sub>2</sub>O<sub>3</sub> for EO at 210 °C was 85 %. It is shown that Ag(100) surface has better O<sub>2</sub> interaction and activated than that of Ag(111) surface, and (100) has a lower activation energy than the side reaction (0.9 eV <em>vs</em> 1.0 eV), facilitates the conversion of ethylene to ethylene oxide. This study provides a new method to design and optimize silver catalysts.","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"29 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539217","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
O bonds and ultimately optimizing the binding strength of intermediates. The results provide an in-depth understanding of the structure–activity relationship on MN4C, and are helpful for the design of single atom catalysts.
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