In this work, a series of coal-based active carbon (CAC) catalysts loaded by A1203 were prepared by sol-gel method and used for the simulta- neous catalytic hydrolysis of carbonyl sulfide (COS) and carbon disulfi...In this work, a series of coal-based active carbon (CAC) catalysts loaded by A1203 were prepared by sol-gel method and used for the simulta- neous catalytic hydrolysis of carbonyl sulfide (COS) and carbon disulfide (CS2) at relatively low temperatures of 30-70 ℃. The influences of calcinations temperatures and operation conditions such as: reaction temperature, 02 concentration, gas hourly space velocity (GHSV) and relative humidity (RH) were also discussed respectively. The results showed that catalysts with 5.0 wt% A1203 calcined at 300 ℃ had supe- rior activity for the simultaneous catalytic hydrolysis of COS and CS2. When the reaction temperature was above 50 ℃, catalytic hydrolysis activity of COS could be enhanced but that of CS2 was inhibited. Too high RH could make the catalytic hydrolysis activities of COS and CS2 decrease. A small amount of 02 introduction could enhance the simultaneous catalytic hydrolysis activities of COS and CS2.展开更多
The activation of H_(2)O is a key step of the COS hydrolysis,which may be tuned by oxygen vacancy defects in the catalysts.Herein,we have introduced Cu into Co_(3)O_(4) to regulate the oxygen vacancy defect content of...The activation of H_(2)O is a key step of the COS hydrolysis,which may be tuned by oxygen vacancy defects in the catalysts.Herein,we have introduced Cu into Co_(3)O_(4) to regulate the oxygen vacancy defect content of the catalysts.In situ DRIFTS and XPS spectra reveal that COS and H_(2)O are adsorbed and activated by oxygen vacancy.The 10 at%Cu doped Co_(3)O_(4) sample(10Cu-Co_(3)O_(4))exhibits the optimal activity,100%of COS conversion at 70℃.The improved oxygen vacancies of CueCo_(3)O_(4) accelerate the activation of H_(2)O to form active -OH.COS binds with hydroxyl to form the intermediate HSCO^(-)_(2),and then the activated-OH on the oxygen vacancy reacts with HSCO^(-)_(2) to form HCO^(-)_(3).Meanwhile,the catalyst exhibits high catalytic stability because copper species(Cu+/Cu^(2+))redox cycle mitigate the sulfation of Co_(3)O_(4)(Co^(2+)/Co^(3+)).Our work offers a promising approach for the rational design of cobalt-related catalysts in the highly efficient hydrolysis COS process.展开更多
The hydrolysis of MgH_(2) delivers high hydrogen capacity(15.2 wt%),which is very attractive for real-time hydrogen supply.However,the formation of a surface passivation Mg(OH)_(2) layer and the large excess of H_(2)O...The hydrolysis of MgH_(2) delivers high hydrogen capacity(15.2 wt%),which is very attractive for real-time hydrogen supply.However,the formation of a surface passivation Mg(OH)_(2) layer and the large excess of H_(2)O required to ensure complete hydrolysis are two key challenges for the MgH_(2) hydrolysis systems.Now,a low-cost method is reported to synthesize MgH_(2)@Mg(BH_(4))_(2) composite via ball-milling MgH_(2) with cheap and widely available B_(2)O_(3)(or B(OH)_(3)).By adding small amounts of B_(2)O_(3),the in-situ formed Mg(BH_(4))_(2) could significantly promote the hydrolysis of MgH_(2).In particular,the MgH_(2)–10 wt%B_(2)O_(3) composite releases 1330.7 mL·g^(−1) H_(2)(close to 80%theoretical hydrogen generation H_(2))in H_(2)O and 1520.4 mL·g^(−1) H_(2)(about 95%)in 0.5 M MgCl_(2) in 60 min at 26℃ with hydrolysis rate of 736.9 mL·g^(−1)·min^(−1) and 960.9 mL·g^(−1)·min^(−1) H_(2) during the first minute of the hydrolysis,respectively.In addition,the MgCl_(2) solution allows repeated use by filtering and exhibits high cycle stability(20 cycles),therefore leading to much reduced capacity loss caused by the excess H_(2)O.We show that by introducing B_(2)O_(3) and recycling the 0.5 M MgCl_(2) solution,the system hydrogen capacity can approach 5.9 wt%,providing a promising hydrogen generation scheme to supply hydrogen to the fuel cells.展开更多
Three diesters of exo- syn-meso-oxabicyclo (2, 2, 1 ) -hept- 5- ene- 2, 3- dicarboxylic acid and three tetraesters of tetrahydrofuran-2, 3, 4, 5-tetracarboxylic acid were synthesized and tested with enantioselective h...Three diesters of exo- syn-meso-oxabicyclo (2, 2, 1 ) -hept- 5- ene- 2, 3- dicarboxylic acid and three tetraesters of tetrahydrofuran-2, 3, 4, 5-tetracarboxylic acid were synthesized and tested with enantioselective hydrolysis catalyzed by pig liver esterase(PLE). The results of the PLEcatalyzed hydrolysis were discussed.展开更多
The Fe3O4 films were prepared by in-situ oxidative hydrolysis on chitosan. The structures and characteristics of the prepared Fe3O4 films were investigated by X-ray diffractometry (XRD), scanning electron microscopy...The Fe3O4 films were prepared by in-situ oxidative hydrolysis on chitosan. The structures and characteristics of the prepared Fe3O4 films were investigated by X-ray diffractometry (XRD), scanning electron microscopy (SEM), atom force microscopy (AFM), vibrating sample magnetometry (VSM) and thermogravimetric-differentia thermal analysis (TG-DTA). The results show that, (1) the as-synthesized Fe3O4 films are pure Fe3O4 with cubic inverse spinel structure; (2) the network structured film can be obtained at lower temperature, and the compact particle film at higher temperature; (3) the prepared Fe3O4 films are super-paramagnetic, and the saturation magnetization is improved with increasing the reaction temperature, which is 49.03 emu/g at 80℃; (4) the temperature of phase transformation from Fe3O4 to a-Fe2O3 is about 495℃. Besides, the formation mechanism of Fe3O4 film was also proposed.展开更多
Microsized single-crystalline Co3O4 has been synthesized by high-temperature hydrolysis of CoCD2H20 at 600℃. The samples were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) an...Microsized single-crystalline Co3O4 has been synthesized by high-temperature hydrolysis of CoCD2H20 at 600℃. The samples were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results reveal that the as-prepared powders are microsized single-crystalline CO3O4 with cubic spinel structure. An increase in the high-temperature hydrolysis time results in the evolution of particle shapes from cube to quasi-sphere, and then to octahedron. The effect of NaCl additive on the surface morphologies of Co3O4 particles was experimentally investigated. The results indicate that the NaCl additive acts as an inert disperse phase in the high-temperature hydrolysis, and prevents the aggregation of Co3O4 particles effectively.展开更多
Si-based hydrolysis material system can be used in mobile/portable hydrogen source applications connected to fuel cells but is limited by alkaline solutions.In the present research,we reported an acid/alkaline free hy...Si-based hydrolysis material system can be used in mobile/portable hydrogen source applications connected to fuel cells but is limited by alkaline solutions.In the present research,we reported an acid/alkaline free hydrolysis systemcombining siliconwith NaBH4.Sampleswith different ratios between Si and NaBH4 are prepared via high energy ball milling and hydrolyzed in deionized water at different temperatures.Synergetic effect between silicon and NaBH4was found in the hydrolysis process.2Si-NaBH4 sample displays the best hydrolysis performances with the hydrogen yield of 1594 ml·g^(−1) in deionized water at 70℃.Thereafter,AlCl3 is added into the 2Si-NaBH4 sample to further improve its comprehensive properties.The effect of AlCl3 content and promotion mechanism of the reaction are explored.2Si-NaBH4-5 wt% AlCl3 sample shows a significant improvement with a high hydrogen yield of 1689 ml·g^(−1) in deionized water at 70℃ and a corresponding conversion rate of 95.8%,indicating that the Si-NaBH4-AlCl3 composite is promising to be a hydrogen source in applications of mobile/portable fuelcell-powered facilities.展开更多
基金supported by the Ministry of Environmental Protection,Public Welfare Project(Contract No 201109034)the National Natural Science Foundation(U1137603)
文摘In this work, a series of coal-based active carbon (CAC) catalysts loaded by A1203 were prepared by sol-gel method and used for the simulta- neous catalytic hydrolysis of carbonyl sulfide (COS) and carbon disulfide (CS2) at relatively low temperatures of 30-70 ℃. The influences of calcinations temperatures and operation conditions such as: reaction temperature, 02 concentration, gas hourly space velocity (GHSV) and relative humidity (RH) were also discussed respectively. The results showed that catalysts with 5.0 wt% A1203 calcined at 300 ℃ had supe- rior activity for the simultaneous catalytic hydrolysis of COS and CS2. When the reaction temperature was above 50 ℃, catalytic hydrolysis activity of COS could be enhanced but that of CS2 was inhibited. Too high RH could make the catalytic hydrolysis activities of COS and CS2 decrease. A small amount of 02 introduction could enhance the simultaneous catalytic hydrolysis activities of COS and CS2.
基金the National Natural Science Foundation of China (92034301,22078063 and 22022804)Major Program of Qingyuan Innovation Laboratory (00121003)the Natural Science Foundation of Fujian Province (2020H6007)。
文摘The activation of H_(2)O is a key step of the COS hydrolysis,which may be tuned by oxygen vacancy defects in the catalysts.Herein,we have introduced Cu into Co_(3)O_(4) to regulate the oxygen vacancy defect content of the catalysts.In situ DRIFTS and XPS spectra reveal that COS and H_(2)O are adsorbed and activated by oxygen vacancy.The 10 at%Cu doped Co_(3)O_(4) sample(10Cu-Co_(3)O_(4))exhibits the optimal activity,100%of COS conversion at 70℃.The improved oxygen vacancies of CueCo_(3)O_(4) accelerate the activation of H_(2)O to form active -OH.COS binds with hydroxyl to form the intermediate HSCO^(-)_(2),and then the activated-OH on the oxygen vacancy reacts with HSCO^(-)_(2) to form HCO^(-)_(3).Meanwhile,the catalyst exhibits high catalytic stability because copper species(Cu+/Cu^(2+))redox cycle mitigate the sulfation of Co_(3)O_(4)(Co^(2+)/Co^(3+)).Our work offers a promising approach for the rational design of cobalt-related catalysts in the highly efficient hydrolysis COS process.
基金supported by the Basic and Applied Basic Research Foundation of Guangdong Province(No.2022A1515011832 and 2021A1515110676)supported by GDAS’Project of Science and Technology Development(2022GDASZH-2022010104,2022GDASZH-2022030604-04).
文摘The hydrolysis of MgH_(2) delivers high hydrogen capacity(15.2 wt%),which is very attractive for real-time hydrogen supply.However,the formation of a surface passivation Mg(OH)_(2) layer and the large excess of H_(2)O required to ensure complete hydrolysis are two key challenges for the MgH_(2) hydrolysis systems.Now,a low-cost method is reported to synthesize MgH_(2)@Mg(BH_(4))_(2) composite via ball-milling MgH_(2) with cheap and widely available B_(2)O_(3)(or B(OH)_(3)).By adding small amounts of B_(2)O_(3),the in-situ formed Mg(BH_(4))_(2) could significantly promote the hydrolysis of MgH_(2).In particular,the MgH_(2)–10 wt%B_(2)O_(3) composite releases 1330.7 mL·g^(−1) H_(2)(close to 80%theoretical hydrogen generation H_(2))in H_(2)O and 1520.4 mL·g^(−1) H_(2)(about 95%)in 0.5 M MgCl_(2) in 60 min at 26℃ with hydrolysis rate of 736.9 mL·g^(−1)·min^(−1) and 960.9 mL·g^(−1)·min^(−1) H_(2) during the first minute of the hydrolysis,respectively.In addition,the MgCl_(2) solution allows repeated use by filtering and exhibits high cycle stability(20 cycles),therefore leading to much reduced capacity loss caused by the excess H_(2)O.We show that by introducing B_(2)O_(3) and recycling the 0.5 M MgCl_(2) solution,the system hydrogen capacity can approach 5.9 wt%,providing a promising hydrogen generation scheme to supply hydrogen to the fuel cells.
基金Supported by the National Natural Science Foundation of China and Schweizerischer National fonds Zur Forderunyder wissenschaft
文摘Three diesters of exo- syn-meso-oxabicyclo (2, 2, 1 ) -hept- 5- ene- 2, 3- dicarboxylic acid and three tetraesters of tetrahydrofuran-2, 3, 4, 5-tetracarboxylic acid were synthesized and tested with enantioselective hydrolysis catalyzed by pig liver esterase(PLE). The results of the PLEcatalyzed hydrolysis were discussed.
基金This work was supported by the National Natural Science Foundation of China under grant No. 50271046.
文摘The Fe3O4 films were prepared by in-situ oxidative hydrolysis on chitosan. The structures and characteristics of the prepared Fe3O4 films were investigated by X-ray diffractometry (XRD), scanning electron microscopy (SEM), atom force microscopy (AFM), vibrating sample magnetometry (VSM) and thermogravimetric-differentia thermal analysis (TG-DTA). The results show that, (1) the as-synthesized Fe3O4 films are pure Fe3O4 with cubic inverse spinel structure; (2) the network structured film can be obtained at lower temperature, and the compact particle film at higher temperature; (3) the prepared Fe3O4 films are super-paramagnetic, and the saturation magnetization is improved with increasing the reaction temperature, which is 49.03 emu/g at 80℃; (4) the temperature of phase transformation from Fe3O4 to a-Fe2O3 is about 495℃. Besides, the formation mechanism of Fe3O4 film was also proposed.
基金Project(50704038) supported by the National Natural Science Foundation of ChinaProject(108170) supported by the Key Foundation of Ministry of Education,China
文摘Microsized single-crystalline Co3O4 has been synthesized by high-temperature hydrolysis of CoCD2H20 at 600℃. The samples were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results reveal that the as-prepared powders are microsized single-crystalline CO3O4 with cubic spinel structure. An increase in the high-temperature hydrolysis time results in the evolution of particle shapes from cube to quasi-sphere, and then to octahedron. The effect of NaCl additive on the surface morphologies of Co3O4 particles was experimentally investigated. The results indicate that the NaCl additive acts as an inert disperse phase in the high-temperature hydrolysis, and prevents the aggregation of Co3O4 particles effectively.
基金financially supported by National Key R&D Program of China(No.2018YFB1502101)the International/Hongkong,Macao&Taiwan Scientific and Technological Innovation Cooperation Project(2019YFH0148)。
文摘Si-based hydrolysis material system can be used in mobile/portable hydrogen source applications connected to fuel cells but is limited by alkaline solutions.In the present research,we reported an acid/alkaline free hydrolysis systemcombining siliconwith NaBH4.Sampleswith different ratios between Si and NaBH4 are prepared via high energy ball milling and hydrolyzed in deionized water at different temperatures.Synergetic effect between silicon and NaBH4was found in the hydrolysis process.2Si-NaBH4 sample displays the best hydrolysis performances with the hydrogen yield of 1594 ml·g^(−1) in deionized water at 70℃.Thereafter,AlCl3 is added into the 2Si-NaBH4 sample to further improve its comprehensive properties.The effect of AlCl3 content and promotion mechanism of the reaction are explored.2Si-NaBH4-5 wt% AlCl3 sample shows a significant improvement with a high hydrogen yield of 1689 ml·g^(−1) in deionized water at 70℃ and a corresponding conversion rate of 95.8%,indicating that the Si-NaBH4-AlCl3 composite is promising to be a hydrogen source in applications of mobile/portable fuelcell-powered facilities.