Hydrogen sulfide(H_(2)S) not only presents significant environmental concerns but also induces severe corrosion in industrial equipment,even at low concentrations.Among various technologies,the selective oxidation of ...Hydrogen sulfide(H_(2)S) not only presents significant environmental concerns but also induces severe corrosion in industrial equipment,even at low concentrations.Among various technologies,the selective oxidation of hydrogen sulfide(SOH_(2)S) to elemental sulfur(S) has emerged as a sustainable and environmentally friendly solution.Due to its unique properties,iron oxide has been extensively investigated as a catalyst for SOH_(2)S;however,rapid deactivation has remained a significant drawback.The causes of iron oxide-based catalysts deactivation mechanisms in SOH_(2)S,including sulfur or sulfate deposition,the transformation of iron species,sintering and excessive oxygen vacancy formation,and active site loss,are thoroughly examined in this review.By focusing on the deactivation mechanisms,this review aims to provide valuable insights into enhancing the stability and efficiency of iron-based catalysts for SOH_(2)S.展开更多
The global commitment to pivoting to sustainable energy and products calls for technology development to utilize solar energy for hydrogen(H_(2))and value-added chemicals production by biomass photoreforming.Herein,a ...The global commitment to pivoting to sustainable energy and products calls for technology development to utilize solar energy for hydrogen(H_(2))and value-added chemicals production by biomass photoreforming.Herein,a novel dual-functional marigold-like Zn_(x)Cd_(1-x)S homojunction has been the production of lactic acid with high-yield and H_(2)with high-efficiency by selective glucose photoreforming.The optimized Zn_(0.3)Cd_(0.7)S exhibits outstanding H_(2)generation(13.64 mmol h^(-1)g^(-1)),glucose conversion(96.40%),and lactic acid yield(76.80%),over 272.80 and 19.21 times higher than that of bare ZnS(0.05 mmol h^(-1)g^(-1))and CdS(0.71 mmol h^(-1)g^(-1))in H_(2)generation,respectively.The marigold-like morphology provides abundant active sites and sufficient substrates accessibility for the photocatalyst,while the specific role of the homojunction formed by hexagonal wurtzite(WZ)and cubic zinc blende(ZB)in photoreforming biomass has been demonstrated by density functional theory(DFT)calculations.Glucose is converted to lactic acid on the WZ surface of Zn_(0.3)Cd_(0.7)S via the photoactive species·O_(2)^(-),while the H_(2)is evolved from protons(H^(+))in H_(2)O on the ZB surface of Zn_(0.3)Cd_(0.7)S.This work paves a promising road for the production of sustainable energy and products by integrating photocatalysis and biorefine.展开更多
The cubic In(OH)3/ZnIn2S4 heterostructures were successfully synthesized via a simple strategy of post-treatment of cubic ZnIn2S4(C-ZIS), and their structures and properties were characterized by X-ray diffraction(XRD...The cubic In(OH)3/ZnIn2S4 heterostructures were successfully synthesized via a simple strategy of post-treatment of cubic ZnIn2S4(C-ZIS), and their structures and properties were characterized by X-ray diffraction(XRD), UV-vis diffuse reflectance spectra(DRS), field emission scanning electron microscopy(FESEM) and transmission electron microscopy(TEM). According to the results, the tofu-like In(OH)3 semiconductor as a new crystal phase appeared in the matrix of C-ZIS and formed a In(OH)3/ZnIn2S4 heterostructure. Compared with pure C-ZIS, the heterostructure exhibits higher photocatalytic activity towards selective oxidation of benzyl alcohol under visible light. The In(OH)3/ZnIn2S4 heterostructure manifests the best and the highest photocatalytic performance via 18 h post-treatment, which achieved nearly 100% selectivity, 35.5%conversion and 34.5% yield. This is ascribed to the formation of In(OH)3/ZnIn2S4 heterostructure to promote the transfer of photogenerated electron-hole pairs and thus efficiently inhibits their recombination, leading to the longer lifetime of photo-induced carriers. Furthermore, a possible photocatalytic mechanism is proposed and discussed. Our current work could boost more interest in researching the semiconductor materials of ternary chalcogenides and enlarging the applications based on cubic ZnIn2S4 heterostructure as visible-light-driven photocatalyst.展开更多
Nanostructured tin dioxide （SnO2） powders were prepared by a sol-gel dialytic process and and the doping of CuO on it was completed by a deposition-precipitation method.The thick film sensors were fabricated from th...Nanostructured tin dioxide （SnO2） powders were prepared by a sol-gel dialytic process and and the doping of CuO on it was completed by a deposition-precipitation method.The thick film sensors were fabricated from the CuO/SnO2 polycrystalline powders.Sensing behavior of the sensor was investigated with various gases including CO,H2,NH3,hexane,acetone,ethanol,methanol and H2S in air.The as-synthesized gas sensor had much better response to H2S than to other gases.At the same time,the CuO/SnO2 sensor had enough sensitivity,together with fast response and recovery,to distinguish H2S from those gases at 160 and 210 ℃.Therefore,it might have promising applications in the future.展开更多
CO_(2) is an important component in the acid gas and it is necessary to study the effect of CO_(2) presence on the oxy-fuel combustion of H_(2)S with particular focus on the formation of carbonyl sulfide(COS).The oxyf...CO_(2) is an important component in the acid gas and it is necessary to study the effect of CO_(2) presence on the oxy-fuel combustion of H_(2)S with particular focus on the formation of carbonyl sulfide(COS).The oxyfuel combustion of acid gas was conducted in a coaxial jet double channel burner.The distribution of flame temperature and products under stoichiometric condition along axial(R=0.0)and radial at about 3.0 mm(R=0.75)were analyzed,respectively.The Chemkin-Pro software was used to analyze the rate of production(ROP)for gas products and the reaction pathway of acid gas combustion.Both experimental and simulation results showed that acid gas combustion experienced the H2S chemical decomposition,H_(2)S oxidation and accompanied by H_(2) oxidation.The CO_(2) presence reduced the peak flame temperature and triggered the formation of COS in the flame area.COS formation at R=0.0 was mainly through the reaction of CO_(2) and CO with sulfur species,whereas at R=0.75 it was through the reaction of CO with sulfur species.The ROP results indicated that H_(2) was mainly from H_(2)O decomposition in the H_(2)S oxidation stage,and COS was formed by the reaction of CO_(2) with H_(2)S.ROP and other detailed analysis further revealed the role of H,OH and SH radicals in each stage of H_(2)S conversion.This study revealed the COS formation mechanisms with CO_(2) presence in the oxy-fuel combustion of H_(2)S and could offer important insights for pollutant control.展开更多
Being abundant and active,Fe_(2)O_(3) is suitable for selective oxidation of H_(2)S.However,its practical application is limited due to the poor sulfur selectivity and rapid deactivation.Herein,we report a facile temp...Being abundant and active,Fe_(2)O_(3) is suitable for selective oxidation of H_(2)S.However,its practical application is limited due to the poor sulfur selectivity and rapid deactivation.Herein,we report a facile template-free hydrothermal method to fabricate porousα-Fe_(2)O_(3)/SnO_(2) composites with hierarchical nanoflower that can obviously improve the catalytic performance of Fe_(2)O_(3).It was disclosed that the synergistic effect betweenα-Fe_(2)O_(3) and SnO_(2) promotes the physico-chemical properties ofα-Fe_(2)O_(3)/SnO_(2) composites.Specifically,the electron transfer between the Fe^(2+)/Fe^(3+)and Sn^(2+)/Sn^(4+)redox couples enhances the reducibility ofα-Fe_(2)O_(3)/SnO_(2) composites.The number of oxygen vacancies is improved when the Fe cations incorporate into SnO_(2) structure,which facilitates the adsorption and activation of oxygen species.Additionally,the porous structure improves the accessibility of H_(2) S to active sites.Among the composites,Fe1 Sn1 exhibits complete H_(2) S conversion with 100%sulfur selectivity at 220℃,better than those of pureα-Fe_(2)O_(3) and SnO2.Moreover,Fe1 Sn1 catalyst shows high stability and water resistance.展开更多
Photocatalytic anaerobic organic oxidation coupled with H_(2)evolution represents an advanced solar energy utilization strategy for the coproduction of clean fuel and fine chemicals.To achieve a high conversion effici...Photocatalytic anaerobic organic oxidation coupled with H_(2)evolution represents an advanced solar energy utilization strategy for the coproduction of clean fuel and fine chemicals.To achieve a high conversion efficiency,the smart design of efficient catalysts by the right combination of semiconductor light harvesters and cocatalyst is highly required.Herein,we report a composite photocatalyst composed of noble metal-free transition metal nitride Ni_(3)FeN decorated on 2D ultrathin ZnIn_(2)S_(4)(ZIS)nanosheets for selective oxidation of aromatic alcohols to aldehydes pairing with H_(2)production.In the composite,ultrathin ZIS serves as a light harvester that greatly shortens the diffusion length of photogenerated charges,while the metallic nitride Ni_(3)FeN acts as an advanced cocatalyst which not only captures the photoelectrons generated from the ultrathin ZIS to promote the charge separation,but also provides active sites to lower the overpotential and accelerate the H_(2)reduction.The best photocatalytic performance is found on ZIS/1.5%M-Ni_(3)FeN,which shows a H_(2)generation rate of 2427.9μmol g^(^(-1))h^(-1)and a benzaldehyde(BAD)production rate of 2460μmol g^(-1)h^(-1),about 7.8-fold as high as that of bare ZIS.This work is anticipated to endorse the exploration of transition metal nitrides as high-performance cocatalysts to promote the coupled photocatalytic organic transformation and H_(2)production.展开更多
H_(2)S selective catalytic oxidation technology is a prospective way for the treatment of low concentration acid gas with simple process operation and low investment. However, undesirable results such as large formati...H_(2)S selective catalytic oxidation technology is a prospective way for the treatment of low concentration acid gas with simple process operation and low investment. However, undesirable results such as large formation of SO_(2) and catalyst deactivation inevitably occur, due to the temperature rise of fixed reaction bed caused by the exothermic reaction. Catalyst with high activity in wide operating temperature window, especially in high temperature range, is urgently needed. In this paper, a series of copper-substituted hexaaluminate catalysts (LaCu_(x), x = 0, 0.5, 1, 1.5, 2, 2.5) were prepared and investigated for the H_(2)S selective oxidation reaction at high temperature conditions (300-550℃). The LaCu_(1) catalyst exhibited excellent catalytic performance and great stability, which was attributed to the best reductive properties and proper pore structure. Besides, two facile deep processing paths were proposed to eliminate the remaining H_(2)S and SO_(2) in the tail gas.展开更多
基金supported by Thailand Science Research and Innovation Fund Chulalongkorn University,Thailand(IND66210014)。
文摘Hydrogen sulfide(H_(2)S) not only presents significant environmental concerns but also induces severe corrosion in industrial equipment,even at low concentrations.Among various technologies,the selective oxidation of hydrogen sulfide(SOH_(2)S) to elemental sulfur(S) has emerged as a sustainable and environmentally friendly solution.Due to its unique properties,iron oxide has been extensively investigated as a catalyst for SOH_(2)S;however,rapid deactivation has remained a significant drawback.The causes of iron oxide-based catalysts deactivation mechanisms in SOH_(2)S,including sulfur or sulfate deposition,the transformation of iron species,sintering and excessive oxygen vacancy formation,and active site loss,are thoroughly examined in this review.By focusing on the deactivation mechanisms,this review aims to provide valuable insights into enhancing the stability and efficiency of iron-based catalysts for SOH_(2)S.
基金supported by the National Natural Science Foundation of China(No.32071713)the Outstanding Youth Foundation Project of Heilongjiang Province of China(JQ2019C001)。
文摘The global commitment to pivoting to sustainable energy and products calls for technology development to utilize solar energy for hydrogen(H_(2))and value-added chemicals production by biomass photoreforming.Herein,a novel dual-functional marigold-like Zn_(x)Cd_(1-x)S homojunction has been the production of lactic acid with high-yield and H_(2)with high-efficiency by selective glucose photoreforming.The optimized Zn_(0.3)Cd_(0.7)S exhibits outstanding H_(2)generation(13.64 mmol h^(-1)g^(-1)),glucose conversion(96.40%),and lactic acid yield(76.80%),over 272.80 and 19.21 times higher than that of bare ZnS(0.05 mmol h^(-1)g^(-1))and CdS(0.71 mmol h^(-1)g^(-1))in H_(2)generation,respectively.The marigold-like morphology provides abundant active sites and sufficient substrates accessibility for the photocatalyst,while the specific role of the homojunction formed by hexagonal wurtzite(WZ)and cubic zinc blende(ZB)in photoreforming biomass has been demonstrated by density functional theory(DFT)calculations.Glucose is converted to lactic acid on the WZ surface of Zn_(0.3)Cd_(0.7)S via the photoactive species·O_(2)^(-),while the H_(2)is evolved from protons(H^(+))in H_(2)O on the ZB surface of Zn_(0.3)Cd_(0.7)S.This work paves a promising road for the production of sustainable energy and products by integrating photocatalysis and biorefine.
基金supported by the Key Projects of Youth Natural Fund in Fujian Universities(JZ160414)the Natural Science Foundation of Fujian Province(2019J01247)
文摘The cubic In(OH)3/ZnIn2S4 heterostructures were successfully synthesized via a simple strategy of post-treatment of cubic ZnIn2S4(C-ZIS), and their structures and properties were characterized by X-ray diffraction(XRD), UV-vis diffuse reflectance spectra(DRS), field emission scanning electron microscopy(FESEM) and transmission electron microscopy(TEM). According to the results, the tofu-like In(OH)3 semiconductor as a new crystal phase appeared in the matrix of C-ZIS and formed a In(OH)3/ZnIn2S4 heterostructure. Compared with pure C-ZIS, the heterostructure exhibits higher photocatalytic activity towards selective oxidation of benzyl alcohol under visible light. The In(OH)3/ZnIn2S4 heterostructure manifests the best and the highest photocatalytic performance via 18 h post-treatment, which achieved nearly 100% selectivity, 35.5%conversion and 34.5% yield. This is ascribed to the formation of In(OH)3/ZnIn2S4 heterostructure to promote the transfer of photogenerated electron-hole pairs and thus efficiently inhibits their recombination, leading to the longer lifetime of photo-induced carriers. Furthermore, a possible photocatalytic mechanism is proposed and discussed. Our current work could boost more interest in researching the semiconductor materials of ternary chalcogenides and enlarging the applications based on cubic ZnIn2S4 heterostructure as visible-light-driven photocatalyst.
文摘Nanostructured tin dioxide （SnO2） powders were prepared by a sol-gel dialytic process and and the doping of CuO on it was completed by a deposition-precipitation method.The thick film sensors were fabricated from the CuO/SnO2 polycrystalline powders.Sensing behavior of the sensor was investigated with various gases including CO,H2,NH3,hexane,acetone,ethanol,methanol and H2S in air.The as-synthesized gas sensor had much better response to H2S than to other gases.At the same time,the CuO/SnO2 sensor had enough sensitivity,together with fast response and recovery,to distinguish H2S from those gases at 160 and 210 ℃.Therefore,it might have promising applications in the future.
基金supported by the National Natural Science Foundation of China(21978092)Chenguang Program by Educational Administration of Shanghai(21CGA35)Yangfan Program by Scientifical Administration of Shanghai(22YF1410300).
文摘CO_(2) is an important component in the acid gas and it is necessary to study the effect of CO_(2) presence on the oxy-fuel combustion of H_(2)S with particular focus on the formation of carbonyl sulfide(COS).The oxyfuel combustion of acid gas was conducted in a coaxial jet double channel burner.The distribution of flame temperature and products under stoichiometric condition along axial(R=0.0)and radial at about 3.0 mm(R=0.75)were analyzed,respectively.The Chemkin-Pro software was used to analyze the rate of production(ROP)for gas products and the reaction pathway of acid gas combustion.Both experimental and simulation results showed that acid gas combustion experienced the H2S chemical decomposition,H_(2)S oxidation and accompanied by H_(2) oxidation.The CO_(2) presence reduced the peak flame temperature and triggered the formation of COS in the flame area.COS formation at R=0.0 was mainly through the reaction of CO_(2) and CO with sulfur species,whereas at R=0.75 it was through the reaction of CO with sulfur species.The ROP results indicated that H_(2) was mainly from H_(2)O decomposition in the H_(2)S oxidation stage,and COS was formed by the reaction of CO_(2) with H_(2)S.ROP and other detailed analysis further revealed the role of H,OH and SH radicals in each stage of H_(2)S conversion.This study revealed the COS formation mechanisms with CO_(2) presence in the oxy-fuel combustion of H_(2)S and could offer important insights for pollutant control.
基金supported by the National Natural Science Fund for Distinguished Young Scholars of China(No.21825801)National Natural Science Foundation of China(Nos.21677036,21878052 and 21773030)。
文摘Being abundant and active,Fe_(2)O_(3) is suitable for selective oxidation of H_(2)S.However,its practical application is limited due to the poor sulfur selectivity and rapid deactivation.Herein,we report a facile template-free hydrothermal method to fabricate porousα-Fe_(2)O_(3)/SnO_(2) composites with hierarchical nanoflower that can obviously improve the catalytic performance of Fe_(2)O_(3).It was disclosed that the synergistic effect betweenα-Fe_(2)O_(3) and SnO_(2) promotes the physico-chemical properties ofα-Fe_(2)O_(3)/SnO_(2) composites.Specifically,the electron transfer between the Fe^(2+)/Fe^(3+)and Sn^(2+)/Sn^(4+)redox couples enhances the reducibility ofα-Fe_(2)O_(3)/SnO_(2) composites.The number of oxygen vacancies is improved when the Fe cations incorporate into SnO_(2) structure,which facilitates the adsorption and activation of oxygen species.Additionally,the porous structure improves the accessibility of H_(2) S to active sites.Among the composites,Fe1 Sn1 exhibits complete H_(2) S conversion with 100%sulfur selectivity at 220℃,better than those of pureα-Fe_(2)O_(3) and SnO2.Moreover,Fe1 Sn1 catalyst shows high stability and water resistance.
基金National Natural Science Foundation of China(21905049 and 22178057)Natural Science Foundation of Fujian Province(2020J01201 and 2021J01197)Award Program for Minjiang Scholar Professorship.S.Liu thanks the support from the Fundamental Research Funds for the Central Universities(Grant No.DUT21RC(3)114).
文摘Photocatalytic anaerobic organic oxidation coupled with H_(2)evolution represents an advanced solar energy utilization strategy for the coproduction of clean fuel and fine chemicals.To achieve a high conversion efficiency,the smart design of efficient catalysts by the right combination of semiconductor light harvesters and cocatalyst is highly required.Herein,we report a composite photocatalyst composed of noble metal-free transition metal nitride Ni_(3)FeN decorated on 2D ultrathin ZnIn_(2)S_(4)(ZIS)nanosheets for selective oxidation of aromatic alcohols to aldehydes pairing with H_(2)production.In the composite,ultrathin ZIS serves as a light harvester that greatly shortens the diffusion length of photogenerated charges,while the metallic nitride Ni_(3)FeN acts as an advanced cocatalyst which not only captures the photoelectrons generated from the ultrathin ZIS to promote the charge separation,but also provides active sites to lower the overpotential and accelerate the H_(2)reduction.The best photocatalytic performance is found on ZIS/1.5%M-Ni_(3)FeN,which shows a H_(2)generation rate of 2427.9μmol g^(^(-1))h^(-1)and a benzaldehyde(BAD)production rate of 2460μmol g^(-1)h^(-1),about 7.8-fold as high as that of bare ZIS.This work is anticipated to endorse the exploration of transition metal nitrides as high-performance cocatalysts to promote the coupled photocatalytic organic transformation and H_(2)production.
基金financially supported by the National Natural Science Foundation of China (Nos. 21976176, 22006148)the Key R&D Program of Shandong province (No. 2019JZZY010506)the Fundamental Research Funds for the Central Universities。
文摘H_(2)S selective catalytic oxidation technology is a prospective way for the treatment of low concentration acid gas with simple process operation and low investment. However, undesirable results such as large formation of SO_(2) and catalyst deactivation inevitably occur, due to the temperature rise of fixed reaction bed caused by the exothermic reaction. Catalyst with high activity in wide operating temperature window, especially in high temperature range, is urgently needed. In this paper, a series of copper-substituted hexaaluminate catalysts (LaCu_(x), x = 0, 0.5, 1, 1.5, 2, 2.5) were prepared and investigated for the H_(2)S selective oxidation reaction at high temperature conditions (300-550℃). The LaCu_(1) catalyst exhibited excellent catalytic performance and great stability, which was attributed to the best reductive properties and proper pore structure. Besides, two facile deep processing paths were proposed to eliminate the remaining H_(2)S and SO_(2) in the tail gas.
