Enhanced photocatalytic N_2 fixation by promoting N_2 adsorption with a co-catalyst
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摘要
Photocatalytic N2 fixation involves a nitrogen reduction reaction on the surface of the photocatalyst to convert N2 into ammonia.Currently,the adsorption of N2 is the limiting step for the N2 reduction reaction on the surface of the catalyst.Based on the concept of photocatalytic water splitting,the photocatalytic efficiency can be greatly enhanced by introducing a co-catalyst.In this report,we proposed a new strategy,namely,the loading of a NiS co-catalyst on CdS nanorods for photocatalytic N2 fixation.Theoretical calculation results indicated that N_2 was effectively adsorbed onto the NiS/CdS surface.Temperature programmed desorption studies confirmed that the N_2 molecules preferred to adsorb onto the NiS/CdS surface.Linear sweep voltammetry results revealed that the overpotential of the N_2 reduction reaction was reduced by loading NiS.Furthermore,transient photocurrent and electrochemical impedance spectroscopy indicated that the charge separation was enhanced by introducing NiS.Photocatalytic N_2 fixation was carried out in the presence of the catalyst dispersed in water without any sacrificial agent.As a result,1.0 wt% NiS/CdS achieved an ammonia production rate of 2.8 and 1.7 mg L-1 for the first hour under full spectrum and visible light(λ>420 nm),respectively.The catalyst demonstrated apparent quantum efficiencies of 0.76%,0.39% and 0.09% at 420,475 and 520 nm,res pectively.This study provides a new method to promote the photocatalytic efficiency of N_2 fixation.
Photocatalytic N2 fixation involves a nitrogen reduction reaction on the surface of the photocatalyst to convert N2 into ammonia.Currently,the adsorption of N2 is the limiting step for the N2 reduction reaction on the surface of the catalyst.Based on the concept of photocatalytic water splitting,the photocatalytic efficiency can be greatly enhanced by introducing a co-catalyst.In this report,we proposed a new strategy,namely,the loading of a NiS co-catalyst on CdS nanorods for photocatalytic N2 fixation.Theoretical calculation results indicated that N_2 was effectively adsorbed onto the NiS/CdS surface.Temperature programmed desorption studies confirmed that the N_2 molecules preferred to adsorb onto the NiS/CdS surface.Linear sweep voltammetry results revealed that the overpotential of the N_2 reduction reaction was reduced by loading NiS.Furthermore,transient photocurrent and electrochemical impedance spectroscopy indicated that the charge separation was enhanced by introducing NiS.Photocatalytic N_2 fixation was carried out in the presence of the catalyst dispersed in water without any sacrificial agent.As a result,1.0 wt% NiS/CdS achieved an ammonia production rate of 2.8 and 1.7 mg L-1 for the first hour under full spectrum and visible light(λ>420 nm),respectively.The catalyst demonstrated apparent quantum efficiencies of 0.76%,0.39% and 0.09% at 420,475 and 520 nm,res pectively.This study provides a new method to promote the photocatalytic efficiency of N_2 fixation.
Photocatalytic N2 fixation involves a nitrogen reduction reaction on the surface of the photocatalyst to convert N2 into ammonia.Currently,the adsorption of N2 is the limiting step for the N2 reduction reaction on the surface of the catalyst.Based on the concept of photocatalytic water splitting,the photocatalytic efficiency can be greatly enhanced by introducing a co-catalyst.In this report,we proposed a new strategy,namely,the loading of a NiS co-catalyst on CdS nanorods for photocatalytic N2 fixation.Theoretical calculation results indicated that N_2 was effectively adsorbed onto the NiS/CdS surface.Temperature programmed desorption studies confirmed that the N_2 molecules preferred to adsorb onto the NiS/CdS surface.Linear sweep voltammetry results revealed that the overpotential of the N_2 reduction reaction was reduced by loading NiS.Furthermore,transient photocurrent and electrochemical impedance spectroscopy indicated that the charge separation was enhanced by introducing NiS.Photocatalytic N_2 fixation was carried out in the presence of the catalyst dispersed in water without any sacrificial agent.As a result,1.0 wt% NiS/CdS achieved an ammonia production rate of 2.8 and 1.7 mg L-1 for the first hour under full spectrum and visible light(λ>420 nm),respectively.The catalyst demonstrated apparent quantum efficiencies of 0.76%,0.39% and 0.09% at 420,475 and 520 nm,res pectively.This study provides a new method to promote the photocatalytic efficiency of N_2 fixation.
引文
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[21]Oshikiri T,Ueno K,Misawa H.Selective dinitrogen conversion to ammonia using water and visible light through plasmon-induced charge separation.Angew Chem Int Ed 2016;55:3942-6.
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[25]Kou J,Lu C,Wang J,et al.Selectivity enhancement in heterogeneous photocatalytic transformations.Chem Rev 2017;117:1445-514.
[26]Zhang P,Wang T,Chang X,et al.Effective charge carrier utilization in photocatalytic conversions.Acc Chem Res 2016;49:911-21.
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[28]Yang J,Wang D,Han H,et al.Roles of cocatalysts in photocatalysis and photoelectrocatalysis.Acc Chem Res 2013;46:1900-9.
[29]Ding C,Shi J,Wang Z,et al.Photoelectrocatalytic water splitting:significance of cocatalysts,electrolyte,and interfaces.ACS Catal 2016;7:675-88.
[30]Liu M,Chen Y,Su J,et al.Photocatalytic hydrogen production using twinned nanocrystals and an unanchored NiSxco-catalyst.Nat Energy 2016;1:16151.
[31]Maeda K,Domen K.Development of novel photocatalyst and cocatalyst materials for water splitting under visible light.Bull Chem Soc Jpn2016;89:627-48.
[32]Kresse G,Hafner J.Ab initio molecular dynamics for liquid metals.Phys Rev B1993;47:558-61.
[33]Kresse G,Furthmüller J.Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set.Comput Mater Sci1996;6:15-50.
[34]Perdew JP,Burke K,Ernzerhof M.Generalized gradient approximation made simple.Phys Rev Lett 1996;77:3865-8.
[35]Kresse G,Joubert D.From ultrasoft pseudopotentials to the projector augmented-wave method.Phys Rev B 1999;59:1758-75.
[36]Bl?chl PE.Projector augmented-wave method.Phys Rev B 1994;50:17953-79.
[37]Monkhorst HJ,Pack JD.Special points for brillouin-zone integrations.Phys Rev B 1976;13:5188-92.
[38]Zhang X,Zhao Z,Zhang W,et al.Surface defects enhanced visible light photocatalytic h2production for Zn-Cd-S solid solution.Small2016;12:793-801.
[39]Nazemi M,Panikkanvalappil SR,El-Sayed MA.Enhancing the rate of electrochemical nitrogen reduction reaction for ammonia synthesis under ambient conditions using hollow gold nanocages.Nano Energy2018;49:316-23.
[40]Han J,Liu Z,Ma Y,et al.Ambient N2fixation to NH3at ambient conditions:using Nb2O5nanofiber as a high-performance electrocatalyst.Nano Energy2018;52:264-70.
[41]Zhao Y,Shi R,Bian X,et al.Ammonia detection methods in photocatalytic and electrocatalytic experiments:How to improve the reliability of NH3production rates?Adv Sci 2019;6:1802109.
[42]Zhao Y,Zhao Y,Shi R,et al.Tuning oxygen vacancies in ultrathin TiO2nanosheets to boost photocatalytic nitrogen fixation up to 700 nm.Adv Mater2019;31:1806482.
[2]Honkala K,Hellman A,Remediakis IN,et al.Ammonia synthesis from firstprinciples calculations.Science 2005;307:555-8.
[3]Schrauzer GN,Guth TD.Photolysis of water and photoreduction of nitrogen on titanium dioxide.J Am Chem Soc 1977;99:7189.
[4]Bickley RI,Vishwanathan V.Photocatalytically induced fixation of molecular nitrogen by near uv radiation.Nature 1979;280:306-8.
[5]Wang S,Ichihara F,Pang H,et al.Nitrogen fixation reaction derived from nanostructured catalytic materials.Adv Funct Mater 2018;28:1803309.
[6]Li H,Li J,Ai Z,et al.Oxygen vacancy-mediated photocatalysis of biocl:reactivity,selectivity,and perspectives.Angew Chem Int Ed 2018;57:122-38.
[7]Liu J,Kelley MS,Wu W,et al.Nitrogenase-mimic iron-containing chalcogels for photochemical reduction of dinitrogen to ammonia.Proc Natl Acad Sci USA2016;113:5530-5.
[8]Zhang N,Jalil A,Wu D,et al.Refining defect states in W18O49by Mo doping:a strategy for tuning N2activation towards solar-driven nitrogen fixation.J Am Chem Soc 2018;140:9434-43.
[9]Zhu D,Zhang L,Ruther RE,et al.Photo-illuminated diamond as a solid-state source of solvated electrons in water for nitrogen reduction.Nat Mater2013;12:836-41.
[10]Li H,Shang J,Ai Z,et al.Efficient visible light nitrogen fixation with biobr nanosheets of oxygen vacancies on the exposed 001 facets.J Am Chem Soc2015;137:6393-9.
[11]Medford AJ,Hatzell MC.Photon-driven nitrogen fixation:current progress,thermodynamic considerations,and future outlook.ACS Catal2017;7:2624-43.
[12]Li H,Shang J,Shi J,et al.Facet-dependent solar ammonia synthesis of biocl nanosheets via a proton-assisted electron transfer pathway.Nanoscale2016;8:1986-93.
[13]Li J,Li H,Zhan G,et al.Solar water splitting and nitrogen fixation with layered bismuth oxyhalides.Acc Chem Res 2017;50:112-21.
[14]Sun S,An Q,Wang W,et al.Efficient photocatalytic reduction of dinitrogen to ammonia on bismuth monoxide quantum dots.J Mater Chem A 2017;5:201-9.
[15]Hirakawa H,Hashimoto M,Shiraishi Y,et al.Photocatalytic conversion of nitrogen to ammonia with water on surface oxygen vacancies of titanium dioxide.J Am Chem Soc 2017;139:10929-36.
[16]Gao X,Wen Y,Qu D,et al.Interference effect of alcohol on nessler’s reagent in photocatalytic nitrogen fixation.ACS Sustain Chem Eng 2018;6:5342-8.
[17]Li X,Wang W,Jiang D,et al.Efficient solar-driven nitrogen fixation over carbon-tungstic-acid hybrids.Chem Eur J 2016;22:13819-22.
[18]Ling C,Niu X,Li Q,et al.Metal-free single atom catalyst for N2fixation driven by visible light.J Am Chem Soc 2018;140:14161-8.
[19]Zhao Y,Zhao Y,Waterhouse GIN,et al.Layered-double-hydroxide nanosheets as efficient visible-light-driven photocatalysts for dinitrogen fixation.Adv Mater 2017;29:1703828.
[20]Lu Y,Yang Y,Zhang T,et al.Photoprompted hot electrons from bulk crosslinked graphene materials and their efficient catalysis for atmospheric ammonia synthesis.ACS Nano 2016;10:10507-15.
[21]Oshikiri T,Ueno K,Misawa H.Selective dinitrogen conversion to ammonia using water and visible light through plasmon-induced charge separation.Angew Chem Int Ed 2016;55:3942-6.
[22]Martirez JMP,Carter EA.Prediction of a low-temperature N2dissociation catalyst exploiting near-ir-to-visible light nanoplasmonics.Sci Adv 2017;3:eaao4710.
[23]Chen X,Shen S,Guo L,et al.Semiconductor-based photocatalytic hydrogen generation.Chem Rev 2010;110:6503-70.
[24]Tong H,Ouyang S,Bi Y,et al.Nano-photocatalytic materials:possibilities and challenges.Adv Mater 2012;24:229-51.
[25]Kou J,Lu C,Wang J,et al.Selectivity enhancement in heterogeneous photocatalytic transformations.Chem Rev 2017;117:1445-514.
[26]Zhang P,Wang T,Chang X,et al.Effective charge carrier utilization in photocatalytic conversions.Acc Chem Res 2016;49:911-21.
[27]Wang J,Xia T,Wang L,et al.Enabling visible-light-driven selective CO2reduction by doping quantum dots:trapping electrons and suppressing H2evolution.Angew Chem Int Edit 2018;57:16447-51.
[28]Yang J,Wang D,Han H,et al.Roles of cocatalysts in photocatalysis and photoelectrocatalysis.Acc Chem Res 2013;46:1900-9.
[29]Ding C,Shi J,Wang Z,et al.Photoelectrocatalytic water splitting:significance of cocatalysts,electrolyte,and interfaces.ACS Catal 2016;7:675-88.
[30]Liu M,Chen Y,Su J,et al.Photocatalytic hydrogen production using twinned nanocrystals and an unanchored NiSxco-catalyst.Nat Energy 2016;1:16151.
[31]Maeda K,Domen K.Development of novel photocatalyst and cocatalyst materials for water splitting under visible light.Bull Chem Soc Jpn2016;89:627-48.
[32]Kresse G,Hafner J.Ab initio molecular dynamics for liquid metals.Phys Rev B1993;47:558-61.
[33]Kresse G,Furthmüller J.Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set.Comput Mater Sci1996;6:15-50.
[34]Perdew JP,Burke K,Ernzerhof M.Generalized gradient approximation made simple.Phys Rev Lett 1996;77:3865-8.
[35]Kresse G,Joubert D.From ultrasoft pseudopotentials to the projector augmented-wave method.Phys Rev B 1999;59:1758-75.
[36]Bl?chl PE.Projector augmented-wave method.Phys Rev B 1994;50:17953-79.
[37]Monkhorst HJ,Pack JD.Special points for brillouin-zone integrations.Phys Rev B 1976;13:5188-92.
[38]Zhang X,Zhao Z,Zhang W,et al.Surface defects enhanced visible light photocatalytic h2production for Zn-Cd-S solid solution.Small2016;12:793-801.
[39]Nazemi M,Panikkanvalappil SR,El-Sayed MA.Enhancing the rate of electrochemical nitrogen reduction reaction for ammonia synthesis under ambient conditions using hollow gold nanocages.Nano Energy2018;49:316-23.
[40]Han J,Liu Z,Ma Y,et al.Ambient N2fixation to NH3at ambient conditions:using Nb2O5nanofiber as a high-performance electrocatalyst.Nano Energy2018;52:264-70.
[41]Zhao Y,Shi R,Bian X,et al.Ammonia detection methods in photocatalytic and electrocatalytic experiments:How to improve the reliability of NH3production rates?Adv Sci 2019;6:1802109.
[42]Zhao Y,Zhao Y,Shi R,et al.Tuning oxygen vacancies in ultrathin TiO2nanosheets to boost photocatalytic nitrogen fixation up to 700 nm.Adv Mater2019;31:1806482.