Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3...Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3)Fe oxide/PANI)with a robust hetero-interface,which significantly improves oxygen evolution activities with an overpotential of 270 mV at 10 mA cm^(-2)and specific activity of 2.08 mA cm_(ECSA)^(-2)at overpotential of 300 mV,3.84-fold that of Ni_(3)Fe oxide.It is revealed that the catalyst–support interaction between Ni_(3)Fe oxide and PANI support enhances the Ni–O covalency via the interfacial Ni–N bond,thus promoting the charge and mass transfer on Ni_(3)Fe oxide.Considering the excellent activity and stability,rechargeable Zn-air batteries with optimum Ni_(3)Fe oxide/PANI are assembled,delivering a low charge voltage of 1.95 V to cycle for 400 h at 10 mA cm^(-2).The regulation of the effect of catalyst–support interaction on catalytic activity provides new possibilities for the future design of highly efficient OER catalysts.展开更多
The current single-atom catalysts(SACs)for medicine still suffer from the limited active site density.Here,we develop a synthetic method capable of increasing both the metal loading and mass-specific activity of SACs ...The current single-atom catalysts(SACs)for medicine still suffer from the limited active site density.Here,we develop a synthetic method capable of increasing both the metal loading and mass-specific activity of SACs by exchanging zinc with iron.The constructed iron SACs(h^(3)-FNC)with a high metal loading of 6.27 wt%and an optimized adjacent Fe distance of~4 A exhibit excellent oxidase-like catalytic performance without significant activity decay after being stored for six months and promising antibacterial effects.Attractively,a“density effect”has been found at a high-enough metal doping amount,at which individual active sites become close enough to interact with each other and alter the electronic structure,resulting in significantly boosted intrinsic activity of single-atomic iron sites in h^(3)-FNCs by 2.3 times compared to low-and medium-loading SACs.Consequently,the overall catalytic activity of h^(3)-FNC is highly improved,with mass activity and metal mass-specific activity that are,respectively,66 and 315 times higher than those of commercial Pt/C.In addition,h^(3)-FNCs demonstrate efficiently enhanced capability in catalyzing oxygen reduction into superoxide anion(O_(2)·^(−))and glutathione(GSH)depletion.Both in vitro and in vivo assays demonstrate the superior antibacterial efficacy of h^(3)-FNCs in promoting wound healing.This work presents an intriguing activity-enhancement effect in catalysts and exhibits impressive therapeutic efficacy in combating bacterial infections.展开更多
Photocatalysis has emerged as an effective approach to sustainably convert biomass into value-added products.CoSe_(2)is a promising nonprecious,efficient cocatalyst for photooxidation,which can facilitate the separati...Photocatalysis has emerged as an effective approach to sustainably convert biomass into value-added products.CoSe_(2)is a promising nonprecious,efficient cocatalyst for photooxidation,which can facilitate the separation of photogenerated electron–holes,increase the reaction rates,and enhance photocatalytic efficiency.In this work,we synthesized a stable and efficient photocatalysis system of CoSe_(2)/g-C_(3)N_(4)through attaching CoSe_(2)on g-C_(3)N_(4)sheets,with a yield of 50.12%for the selective photooxidation of xylose to xylonic acid.Under light illumination,the photogenerated electrons were prone to migrating from g-C_(3)N_(4)to CoSe_(2)due to the higher work function of CoSe_(2),resulting in the accelerated separation of photogenerated electron–holes and the promoted photooxidation.Herein,this study reveals the unique function of CoSe_(2),which can significantly promote oxygen adsorption,work as an electron sink and accelerate the generation of ·O_(2)^(-),thereby improving the selectivity toward xylonic acid over other by-products.This work provides useful insights into the design of selective photocatalysts by engineering g-C_(3)N_(4)for biomass high-value utilization.展开更多
Biomass-derived heteroatom self-doped cathode catalysts has attracted considerable interest for electrochemical advanced oxidation processes(EAOPs)due to its high performance and sustainable synthesis.Herein,we illust...Biomass-derived heteroatom self-doped cathode catalysts has attracted considerable interest for electrochemical advanced oxidation processes(EAOPs)due to its high performance and sustainable synthesis.Herein,we illustrated the morphological fates of waste leaf-derived graphitic carbon(WLGC)produced from waste ginkgo leaves via pyrolysis temperature regulation and used as bifunctional cathode catalyst for simultaneous H_(2)O_(2) electrochemical generation and organic pollutant degradation,discovering S/N-self-doping shown to facilitate a synergistic effect on reactive oxygen species(ROS)generation.Under the optimum temperature of 800℃,the WLGC exhibited a H_(2)O_(2) selectivity of 94.2%and tetracycline removal of 99.3%within 60 min.Density functional theory calculations and in-situ Fourier transformed infrared spectroscopy verified that graphitic N was the critical site for H_(2)O_(2) generation.While pyridinic N and thiophene S were the main active sites responsible for OH generation,N vacancies were the active sites to produce ^(1)O_(2) from O_(2).The performance of the novel cathode for tetracycline degradation remains well under a wide pH range(3–11),maintaining excellent stability in 10 cycles.It is also industrially applicable,achieving satisfactory performance treating in real water matrices.This system facilitates both radical and non-radical degradation,offering valuable advances in the preparation of cost-effective and sustainable electrocatalysts and hold strong potentials in metal-free EAOPs for organic pollutant degradation.展开更多
CO_(2) photoreduction into carbon-based chemicals has been considered as an appropriate way to alleviate the energy issue and greenhouse effect.Herein,the 5,10,15,20-tetra(4-carboxyphenyl)porphyrin cobalt(II)(CoTCPP)h...CO_(2) photoreduction into carbon-based chemicals has been considered as an appropriate way to alleviate the energy issue and greenhouse effect.Herein,the 5,10,15,20-tetra(4-carboxyphenyl)porphyrin cobalt(II)(CoTCPP)has been integrated with BiOBr microspheres and formed the CoTCPP/BiOBr composite.The as-prepared CoTCPP/BiOBr-2 composite shows optimized photocatalytic performance for CO_(2) conversion into CO and CH_(4) upon irradiation with 300 W Xe lamp,which is 2.03 and 2.58 times compared to that of BiOBr,respectively.The introduced CoTCPP significantly enhanced light absorption properties,promoted rapid separation of photogenerated carriers and boosted the chemisorption of CO_(2) molecules.The metal Co^(2+) at the center of the porphyrin molecules also acts as adsorption center for CO_(2) molecules,accelerating the CO_(2) conversion into CO and CH_(4).The possible mechanism of CO_(2) photoreduction was explored by in-situ FT-IR spectra.This work offers a new possibility for the preparation of advanced photocatalysts.展开更多
Direct seawater splitting has emerged as a popular and promising research direction for synthesising clean,green,non-polluting,and sustainable hydrogen energy without depending on high-purity water in the face of the ...Direct seawater splitting has emerged as a popular and promising research direction for synthesising clean,green,non-polluting,and sustainable hydrogen energy without depending on high-purity water in the face of the world’s shortage of fossil energy.However,efficient seawater splitting is hindered by slow kinetics caused by the ultra-low conductivity and the presence of bacteria,microorganisms,and stray ions in seawater.Additionally,producing hydrogen on an industrial scale is challenging due to the high production cost.The present review addresses these challenges from the catalyst point of view,namely,that designing catalysts with high catalytic activity and stability can directly affect the rate and effect of seawater splitting.From the ion transfer perspective,designing membranes can block harmful ions,improving the stability of seawater splitting.From the energy point of view,mixed seawater systems and self-powered systems also provide new and low-energy research systems for seawater splitting.Finally,ideas and directions for further research on direct seawater splitting in the future are pointed out,with the aim of achieving low-cost and high-efficiency hydrogen production.展开更多
Developing a cost-effective and environmentally friendly process for the production of valuable chemicals from abundant herbal biomass receives great attentions in recent years.Herein,taking advantage of the“lignin f...Developing a cost-effective and environmentally friendly process for the production of valuable chemicals from abundant herbal biomass receives great attentions in recent years.Herein,taking advantage of the“lignin first”strategy,corn straw is converted to valuable chemicals including lignin monomers,furfural and 5-methoxymethylfurfural via a two steps process.The key of this research lies in the development of a green and low-cost catalytic process utilizing magnetic Raney Ni catalyst and high boiling point ethylene glycol.The utilization of neat ethylene glycol as the sole slovent under atmospheric conditions obviates the need for additional additives,thereby facilitating the entire process to be conducted in glass flasks and rendering it highly convenient for scaling up.In the initial step,depolymerization of corn straw lignin resulted in a monomer yield of 18.1 wt%.Subsequently,in a dimethyl carbonate system,the carbohydrate component underwent complete conversion in a one-pot process,yielding furfural and 5-methoxymethylfurfural as the primary products with an impressive yield of 47.7%.展开更多
Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal int...Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal into NiFe-based catalysts to construct asymmetrical M-NiFe units,the d-orbital and electronic structures can be adjusted,which is an important strategy to achieve sufficient oxygen evolution reaction(OER)performance in AEMWEs.Herein,the ternary NiFeM(M:La,Mo)catalysts featured with distinct M-NiFe units and varying d-orbitals are reported in this work.Experimental and theoretical calculation results reveal that the doping of La leads to optimized hybridization between d orbital in NiFeM and 2p in oxygen,resulting in enhanced adsorption strength of oxygen intermediates,and reduced rate-determining step energy barrier,which is responsible for the enhanced OER performance.More critically,the obtained NiFeLa catalyst only requires 1.58 V to reach 1 A cm^(−2) in an anion exchange membrane electrolyzer and demonstrates excellent long-term stability of up to 600 h.展开更多
分析Ti-β分子筛催化1-己烯环氧化反应过程中的失活的原因,研究其失活过程及再生方法;采用^(13)C MAS NMR和GC-MS等手段分析Ti-β分子筛的积炭情况,并采用XPS、UV-Vis和EDX等手段研究其钛物种变化;进一步以二甲基亚砜溶剂处理失活Ti-β...分析Ti-β分子筛催化1-己烯环氧化反应过程中的失活的原因,研究其失活过程及再生方法;采用^(13)C MAS NMR和GC-MS等手段分析Ti-β分子筛的积炭情况,并采用XPS、UV-Vis和EDX等手段研究其钛物种变化;进一步以二甲基亚砜溶剂处理失活Ti-β分子筛,对其进行再生研究。结果表明:Ti-β分子筛循环使用10次以后,1-己烯转化率降低至新鲜剂的30%以下;在此过程中,Ti-β分子筛中的部分骨架钛转化为非骨架钛,同时1,2-己二醇副产物堵塞孔道或者覆盖活性中心,两者共同导致Ti-β分子筛失活。以二甲基亚砜在160℃条件下对失活的Ti-β分子筛处理可以脱除大部分吸附的1,2-己二醇,使其催化1-己烯环氧化反应的活性恢复至新鲜剂的83%。展开更多
基金Research Institute for Smart Energy(CDB2)the grant from the Research Institute for Advanced Manufacturing(CD8Z)+4 种基金the grant from the Carbon Neutrality Funding Scheme(WZ2R)at The Hong Kong Polytechnic Universitysupport from the Hong Kong Polytechnic University(CD9B,CDBZ and WZ4Q)the National Natural Science Foundation of China(22205187)Shenzhen Municipal Science and Technology Innovation Commission(JCYJ20230807140402006)Start-up Foundation for Introducing Talent of NUIST and Natural Science Foundation of Jiangsu Province of China(BK20230426).
文摘Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3)Fe oxide/PANI)with a robust hetero-interface,which significantly improves oxygen evolution activities with an overpotential of 270 mV at 10 mA cm^(-2)and specific activity of 2.08 mA cm_(ECSA)^(-2)at overpotential of 300 mV,3.84-fold that of Ni_(3)Fe oxide.It is revealed that the catalyst–support interaction between Ni_(3)Fe oxide and PANI support enhances the Ni–O covalency via the interfacial Ni–N bond,thus promoting the charge and mass transfer on Ni_(3)Fe oxide.Considering the excellent activity and stability,rechargeable Zn-air batteries with optimum Ni_(3)Fe oxide/PANI are assembled,delivering a low charge voltage of 1.95 V to cycle for 400 h at 10 mA cm^(-2).The regulation of the effect of catalyst–support interaction on catalytic activity provides new possibilities for the future design of highly efficient OER catalysts.
基金supported by the National Key Research and Development Program of China(Grant No.2022YFB3804500)the National Natural Science Foundation of China(Grant No.52202352,22335006)+4 种基金the Shanghai Municipal Health Commission(Grant No.20224Y0010)the CAMS Innovation Fund for Medical Sciences(Grant No.2021-I2M-5-012)the Basic Research Program of Shanghai Municipal Government(Grant No.21JC1406000)the Fundamental Research Funds for the Central Universities(Grant No.22120230237,2023-3-YB-11,22120220618)the Basic Research Program of Shanghai Municipal Government(23DX1900200).
文摘The current single-atom catalysts(SACs)for medicine still suffer from the limited active site density.Here,we develop a synthetic method capable of increasing both the metal loading and mass-specific activity of SACs by exchanging zinc with iron.The constructed iron SACs(h^(3)-FNC)with a high metal loading of 6.27 wt%and an optimized adjacent Fe distance of~4 A exhibit excellent oxidase-like catalytic performance without significant activity decay after being stored for six months and promising antibacterial effects.Attractively,a“density effect”has been found at a high-enough metal doping amount,at which individual active sites become close enough to interact with each other and alter the electronic structure,resulting in significantly boosted intrinsic activity of single-atomic iron sites in h^(3)-FNCs by 2.3 times compared to low-and medium-loading SACs.Consequently,the overall catalytic activity of h^(3)-FNC is highly improved,with mass activity and metal mass-specific activity that are,respectively,66 and 315 times higher than those of commercial Pt/C.In addition,h^(3)-FNCs demonstrate efficiently enhanced capability in catalyzing oxygen reduction into superoxide anion(O_(2)·^(−))and glutathione(GSH)depletion.Both in vitro and in vivo assays demonstrate the superior antibacterial efficacy of h^(3)-FNCs in promoting wound healing.This work presents an intriguing activity-enhancement effect in catalysts and exhibits impressive therapeutic efficacy in combating bacterial infections.
基金financial support by National Key Research and Development Project(Grant No.2023YFE0109600)Guangzhou Key Research and Development Program(Grant No.2023B03J1330)+5 种基金National Program for Support of Topnotch Young Professionals(Grant No.x2qsA4210090)Guangzhou Basic and Applied Basic Research Foundation(Grant No.2024A04J3413)National Natural Science Foundation of China(Grant No.32201499)State Key Laboratory of Pulp and Paper Engineering(Grant Nos.2023PY01 and 202215)Guangdong Basic and Applied Basic Research Foundation(Grant Nos.2023A1515012519 and 2023B1515040013)China Postdoctoral Science Foundation(Grant No.2023M732021).
文摘Photocatalysis has emerged as an effective approach to sustainably convert biomass into value-added products.CoSe_(2)is a promising nonprecious,efficient cocatalyst for photooxidation,which can facilitate the separation of photogenerated electron–holes,increase the reaction rates,and enhance photocatalytic efficiency.In this work,we synthesized a stable and efficient photocatalysis system of CoSe_(2)/g-C_(3)N_(4)through attaching CoSe_(2)on g-C_(3)N_(4)sheets,with a yield of 50.12%for the selective photooxidation of xylose to xylonic acid.Under light illumination,the photogenerated electrons were prone to migrating from g-C_(3)N_(4)to CoSe_(2)due to the higher work function of CoSe_(2),resulting in the accelerated separation of photogenerated electron–holes and the promoted photooxidation.Herein,this study reveals the unique function of CoSe_(2),which can significantly promote oxygen adsorption,work as an electron sink and accelerate the generation of ·O_(2)^(-),thereby improving the selectivity toward xylonic acid over other by-products.This work provides useful insights into the design of selective photocatalysts by engineering g-C_(3)N_(4)for biomass high-value utilization.
基金financially supported by National Key R&D Program International Cooperation Project(2023YFE0108100)Natural Science Foundation of China(No.52170085)+2 种基金Key Project of Natural Science Foundation of Tianjin(No.21JCZDJC00320)Tianjin Post-graduate Students Research and Innovation Project(2021YJSB013)Fundamental Research Funds for the Central Universities,Nankai University.
文摘Biomass-derived heteroatom self-doped cathode catalysts has attracted considerable interest for electrochemical advanced oxidation processes(EAOPs)due to its high performance and sustainable synthesis.Herein,we illustrated the morphological fates of waste leaf-derived graphitic carbon(WLGC)produced from waste ginkgo leaves via pyrolysis temperature regulation and used as bifunctional cathode catalyst for simultaneous H_(2)O_(2) electrochemical generation and organic pollutant degradation,discovering S/N-self-doping shown to facilitate a synergistic effect on reactive oxygen species(ROS)generation.Under the optimum temperature of 800℃,the WLGC exhibited a H_(2)O_(2) selectivity of 94.2%and tetracycline removal of 99.3%within 60 min.Density functional theory calculations and in-situ Fourier transformed infrared spectroscopy verified that graphitic N was the critical site for H_(2)O_(2) generation.While pyridinic N and thiophene S were the main active sites responsible for OH generation,N vacancies were the active sites to produce ^(1)O_(2) from O_(2).The performance of the novel cathode for tetracycline degradation remains well under a wide pH range(3–11),maintaining excellent stability in 10 cycles.It is also industrially applicable,achieving satisfactory performance treating in real water matrices.This system facilitates both radical and non-radical degradation,offering valuable advances in the preparation of cost-effective and sustainable electrocatalysts and hold strong potentials in metal-free EAOPs for organic pollutant degradation.
基金financially supported by National Natural Science Foundation of China(Nos.22138011,22108106 and 22108108)China Postdoctoral Science Foundation(Nos.2022M721380 and 2020M680065)Hong Kong Scholar Program(XJ2021021).
文摘CO_(2) photoreduction into carbon-based chemicals has been considered as an appropriate way to alleviate the energy issue and greenhouse effect.Herein,the 5,10,15,20-tetra(4-carboxyphenyl)porphyrin cobalt(II)(CoTCPP)has been integrated with BiOBr microspheres and formed the CoTCPP/BiOBr composite.The as-prepared CoTCPP/BiOBr-2 composite shows optimized photocatalytic performance for CO_(2) conversion into CO and CH_(4) upon irradiation with 300 W Xe lamp,which is 2.03 and 2.58 times compared to that of BiOBr,respectively.The introduced CoTCPP significantly enhanced light absorption properties,promoted rapid separation of photogenerated carriers and boosted the chemisorption of CO_(2) molecules.The metal Co^(2+) at the center of the porphyrin molecules also acts as adsorption center for CO_(2) molecules,accelerating the CO_(2) conversion into CO and CH_(4).The possible mechanism of CO_(2) photoreduction was explored by in-situ FT-IR spectra.This work offers a new possibility for the preparation of advanced photocatalysts.
基金support by National Key Research and Development Program of China(2022YFB3803502)National Natural Science Foundation of China(52103076)+5 种基金Science and Technology Commission of Shanghai Municipality(23ZR1400300)special fund of Beijing Key Laboratory of Indoor Air Quality Evaluat ion and Control(NO.BZ0344KF21-02)State Key Laboratory of Electrical Insulation and Power Equipment(EIPE22203)JLF is a member of LSRE-LCM–Laboratory of Separation and Reaction Engineering-Laboratory of Catalysis and Materials,supported by national funds through FCT/MCTES(PIDDAC):LSRE-LCM,UIDB/50020/2020(DOI:10.54499/UIDB/50020/2020)UIDP/50020/2020(DOI:10.54499/UIDP/50020/2020)ALiCE,LA/P/0045/2020(DOI:10.54499/LA/P/0045/2020).
文摘Direct seawater splitting has emerged as a popular and promising research direction for synthesising clean,green,non-polluting,and sustainable hydrogen energy without depending on high-purity water in the face of the world’s shortage of fossil energy.However,efficient seawater splitting is hindered by slow kinetics caused by the ultra-low conductivity and the presence of bacteria,microorganisms,and stray ions in seawater.Additionally,producing hydrogen on an industrial scale is challenging due to the high production cost.The present review addresses these challenges from the catalyst point of view,namely,that designing catalysts with high catalytic activity and stability can directly affect the rate and effect of seawater splitting.From the ion transfer perspective,designing membranes can block harmful ions,improving the stability of seawater splitting.From the energy point of view,mixed seawater systems and self-powered systems also provide new and low-energy research systems for seawater splitting.Finally,ideas and directions for further research on direct seawater splitting in the future are pointed out,with the aim of achieving low-cost and high-efficiency hydrogen production.
基金supported by the Fundamental Research Funds for the Central Universities(QNTD202302)National Natural Science Foundation of China(22378024)the Foreign expert program(G2022109001L).
文摘Developing a cost-effective and environmentally friendly process for the production of valuable chemicals from abundant herbal biomass receives great attentions in recent years.Herein,taking advantage of the“lignin first”strategy,corn straw is converted to valuable chemicals including lignin monomers,furfural and 5-methoxymethylfurfural via a two steps process.The key of this research lies in the development of a green and low-cost catalytic process utilizing magnetic Raney Ni catalyst and high boiling point ethylene glycol.The utilization of neat ethylene glycol as the sole slovent under atmospheric conditions obviates the need for additional additives,thereby facilitating the entire process to be conducted in glass flasks and rendering it highly convenient for scaling up.In the initial step,depolymerization of corn straw lignin resulted in a monomer yield of 18.1 wt%.Subsequently,in a dimethyl carbonate system,the carbohydrate component underwent complete conversion in a one-pot process,yielding furfural and 5-methoxymethylfurfural as the primary products with an impressive yield of 47.7%.
基金financially supported by the National Natural Science Foundation of China(22309137,22279095)Open subject project State Key Laboratory of New Textile Materials and Advanced Processing Technologies(FZ2023001).
文摘Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal into NiFe-based catalysts to construct asymmetrical M-NiFe units,the d-orbital and electronic structures can be adjusted,which is an important strategy to achieve sufficient oxygen evolution reaction(OER)performance in AEMWEs.Herein,the ternary NiFeM(M:La,Mo)catalysts featured with distinct M-NiFe units and varying d-orbitals are reported in this work.Experimental and theoretical calculation results reveal that the doping of La leads to optimized hybridization between d orbital in NiFeM and 2p in oxygen,resulting in enhanced adsorption strength of oxygen intermediates,and reduced rate-determining step energy barrier,which is responsible for the enhanced OER performance.More critically,the obtained NiFeLa catalyst only requires 1.58 V to reach 1 A cm^(−2) in an anion exchange membrane electrolyzer and demonstrates excellent long-term stability of up to 600 h.
文摘分析Ti-β分子筛催化1-己烯环氧化反应过程中的失活的原因,研究其失活过程及再生方法;采用^(13)C MAS NMR和GC-MS等手段分析Ti-β分子筛的积炭情况,并采用XPS、UV-Vis和EDX等手段研究其钛物种变化;进一步以二甲基亚砜溶剂处理失活Ti-β分子筛,对其进行再生研究。结果表明:Ti-β分子筛循环使用10次以后,1-己烯转化率降低至新鲜剂的30%以下;在此过程中,Ti-β分子筛中的部分骨架钛转化为非骨架钛,同时1,2-己二醇副产物堵塞孔道或者覆盖活性中心,两者共同导致Ti-β分子筛失活。以二甲基亚砜在160℃条件下对失活的Ti-β分子筛处理可以脱除大部分吸附的1,2-己二醇,使其催化1-己烯环氧化反应的活性恢复至新鲜剂的83%。
