The interactions and structures of the urea-water system are studied by an all-atom molecular dynamics （MD） simulation. The hydrogen-bonding network and the radial distribution functions are adopted in MD simulation...The interactions and structures of the urea-water system are studied by an all-atom molecular dynamics （MD） simulation. The hydrogen-bonding network and the radial distribution functions are adopted in MD simulations. The structures of urea-water mixtures can be classified into different regions from the analysis of the hydrogen-bonding network. The urea molecule shows the certain tendency to the self-aggregate with the mole fraction of urea increasing. Moreover, the results of the MD simulations are also compare with the chemical shifts and viscosities of the urea aqueous solutions, and the statistical results of the average number hydrogen bonds in the MD simulations are in agreement with the experiment data such as chemical shifts of the hydrogen atom and viscosity.展开更多
The thermolysis of urea-water solution and its product, HNCO hydrolysis is investigated in a dual-reactor system. For the thermal decomposition below about 1073 K, the main products are ammonia (NH3) and isocyanic aci...The thermolysis of urea-water solution and its product, HNCO hydrolysis is investigated in a dual-reactor system. For the thermal decomposition below about 1073 K, the main products are ammonia (NH3) and isocyanic acid (HNCO) whereas at higher temperatures the oxidation processes take effect and the products include a low concentration of nitric oxide (NO) and nitrous oxide (N2O). The gas HNCO is quite stable and a high yield of HNCO is observed. The ratio of NH3 to HNCO increases from approximately 1.2 to 1.7 with the temperature. The chemical analysis shows that H radical is in favor of HNCO hydrolysis by instigating the reaction HNCO+H·→·NH2+CO and high temperature has positive effect on H radical. The hydrolysis of HNCO over an alumina catalyst made using a sol-gel process (designated as γ-Al2O3) is investigated. The conversion of HNCO is high even at the high space velocities (6×105 h-1) and low temperatures (393–673 K) in the tests with catalysts, which enhances HNCO hydrolysis and raises the ratio of NH3 to HNCO to approximately 100. The pure γ-Al2O3 shows a better catalytic performance than CuO/γ-Al2O3. The addition of CuO not only reduces the surface area but also decreases the Lewis acid sites which are recognized to have a positive effect on the catalytic activity. The apparent activation energy of the hydrolysis reaction amounts to about 25 kJ/mol in 393–473 K while 13 kJ/mol over 473 K. The overall hydrolysis reaction rate on catalysts is mainly determined by external and internal mass-transfer limitations.展开更多
电催化尿素氧化(UOR)替代动力学缓慢的析氧反应(OER)为高效制氢提供了新的思路。本研究通过简单的二次水热法制备了三维Ni_(3)S_(2)/NF微球催化剂(3D-Ni_(3)S_(2)/NF),由于独特的3D结构为UOR提供了高度开放的活性区域,并加快了电荷转移...电催化尿素氧化(UOR)替代动力学缓慢的析氧反应(OER)为高效制氢提供了新的思路。本研究通过简单的二次水热法制备了三维Ni_(3)S_(2)/NF微球催化剂(3D-Ni_(3)S_(2)/NF),由于独特的3D结构为UOR提供了高度开放的活性区域,并加快了电荷转移速率,3D-Ni_(3)S_(2)/NF表现出明显优于1D,2D-Ni_(3)S_(2)/NF电催化氧化尿素的活性。在1 mol L^(-1)KOH+0.33 mol L^(-1)尿素电解质溶液,3D-Ni_(3)S_(2)/NF电催化尿素氧化达到100 mA cm^(-2)的电流密度的电位仅需1.38 V vs.RHE,比OER电位减少了250 mV,同时在24 h稳定性测试中表现出良好的耐久性。此外,全尿素辅助制氢只需1.66 V即可达到50 mA cm^(-2),表现出比传统电解水(1.86 V)更低的电位。展开更多
电催化水分解是实现绿色制氢的理想方法之一.然而,阳极析氧反应(OER)固有的缓慢动力学和高理论电压(1.23V),使得电解水制氢的能效受到严重限制.采用理论电位更低和热力学更有利的小分子氧化反应替代OER过程,可以在降低电能耗的同时降解...电催化水分解是实现绿色制氢的理想方法之一.然而,阳极析氧反应(OER)固有的缓慢动力学和高理论电压(1.23V),使得电解水制氢的能效受到严重限制.采用理论电位更低和热力学更有利的小分子氧化反应替代OER过程,可以在降低电能耗的同时降解污染物或生成有附加值的产物,能够带来多重效益.尿素氧化反应(UOR)具有较低的理论电压(0.37V),是替代OER的潜在反应之一.然而,UOR中复杂的六电子转移严重阻碍了尿素电解的整体效率.因此,设计经济且高效的电催化剂来促进UOR固有的缓慢动力学过程非常必要.硒化镍具有电子构型多样和结构调控灵活等优点,被认为是有效的UOR催化剂.然而,UOR过程涉及催化剂表面多种反应中间体的吸附/解吸,单相催化剂要同时满足多种反应中间的吸附/解吸是一项艰巨的挑战.众所周知,非均相电催化涉及电子转移以及电催化剂表面反应物和产物的吸附和解吸.因此,催化剂的电催化性能在很大程度上取决于材料表面的电子特性.通过构建异质结构是一种有效策略,可以调节电催化剂的电子结构,优化反应中间体的化学吸附行为,实现不同组份高效协同电催化.研究表明,通过界面工程优化结构和电子特性可进一步促进UOR的动力学.MoSe_(2)具有良好的稳定性和导电性,与镍基催化剂组合构建异质结构能够改善电催化反应中的催化动力学.本文通过简单的水热和低温硒化方法构建了异质NiSe_(2)/MoSe_(2)微球作为UOR的电催化剂.差分电荷密度和Mulliken电荷分析结果表明,MoSe_(2)与NiSe_(2)的耦合引起界面处的电荷重新分布,促使电子从NiSe_(2)向MoSe_(2)转移,更容易形成高价态Ni(NiOOH)活性物种.另外,异质界面的构建优化了催化剂表面的电子结构并调节d带中心,改变反应途径,降低反应能垒,从而提高UOR的反应活性.异质结NiSe_(2)/MoSe_(2)微球由于其独特的结构特征、强的协同耦合作用、增加的活性中心和高含量的高价Ni3+物种的综合优势而具有高效的催化性能.当负载在玻碳电极上时,仅需1.33 V的电压就能驱动10 m Acm^(-2)的电流密度,该活性优于大多数已报道的非贵金属UOR催化剂.将NiSe_(2)/MoSe_(2)催化剂组装到UOR//HER电解槽中时,NiSe_(2)/MoSe_(2)|Pt/C具有较低的操作电压和长期稳定性,在1.47 V的电池电压下电流密度达到10 m Acm^(-2),比单纯的水电解降低了约220 m V.与OER相比,热力学上有利的UOR可以作为阳极OER替代反应.综上,本文为能源/环境相关的催化反应提供了一个有效的催化剂体系,对构建高效异质结催化系统具有借鉴意义.展开更多
为探究影响柴油机排气管尿素水溶液(urea water solution,UWS)雾化效果的因素,搭建了UWS喷射试验台架,通过激光粒度仪测得尿素液滴粒径分布,并运用Rosin-Rammler函数对试验获得的累积粒径分布进行非线性拟合,利用计算流体力学(computati...为探究影响柴油机排气管尿素水溶液(urea water solution,UWS)雾化效果的因素,搭建了UWS喷射试验台架,通过激光粒度仪测得尿素液滴粒径分布,并运用Rosin-Rammler函数对试验获得的累积粒径分布进行非线性拟合,利用计算流体力学(computational fluid dynamics,CFD)软件对柴油机负荷工况、UWS喷射温度和排气管壁温3种不同因素对UWS喷雾雾化特征、NH3浓度分布及液膜形成的影响进行仿真计算。结果表明:低负荷工况下的排气流量和温度低,UWS喷入量少,尿素液滴分解NH3的速率较低,80 ms时刻NH3主要分布在排气管中游;中高负荷工况,排气温度高、UWS喷入量多,有利于尿素蒸发热解生成NH3,该时刻NH3浓度区域偏离轴线,贴近排气管上表面;喷雾液滴粒径随UWS喷射温度的升高而减小,范围在1~12μm,空间内NH3浓度小幅增加,液膜沉积率随喷射温度升高显著降低;排气管壁温对UWS喷雾液滴粒径和蒸发热解速率影响较大,壁温升高加快了液滴粒径减小的速度,当壁面温度为473K时,150ms时刻下液滴粒径主要集中在30μm以下,附着壁面的液膜厚度明显减小直至消失,尿素结晶问题得以改善。展开更多
基金This work was supported by the National Natural Science Foundation of China （No.20903026）, the Doctoral Scientific Research Foundation of the Natural Science Foundation of Guangdong Province （No.7301567）, and the Research Foundation of Guangdong Pharmaceutical University （No.2006YKX05）.
文摘The interactions and structures of the urea-water system are studied by an all-atom molecular dynamics （MD） simulation. The hydrogen-bonding network and the radial distribution functions are adopted in MD simulations. The structures of urea-water mixtures can be classified into different regions from the analysis of the hydrogen-bonding network. The urea molecule shows the certain tendency to the self-aggregate with the mole fraction of urea increasing. Moreover, the results of the MD simulations are also compare with the chemical shifts and viscosities of the urea aqueous solutions, and the statistical results of the average number hydrogen bonds in the MD simulations are in agreement with the experiment data such as chemical shifts of the hydrogen atom and viscosity.
基金Project supported by the National High-Tech Research and Development Program (863) of China (No. 2009AA05Z301)the National Basic Research Program (973) of China (No. 2006CB-200303)
文摘The thermolysis of urea-water solution and its product, HNCO hydrolysis is investigated in a dual-reactor system. For the thermal decomposition below about 1073 K, the main products are ammonia (NH3) and isocyanic acid (HNCO) whereas at higher temperatures the oxidation processes take effect and the products include a low concentration of nitric oxide (NO) and nitrous oxide (N2O). The gas HNCO is quite stable and a high yield of HNCO is observed. The ratio of NH3 to HNCO increases from approximately 1.2 to 1.7 with the temperature. The chemical analysis shows that H radical is in favor of HNCO hydrolysis by instigating the reaction HNCO+H·→·NH2+CO and high temperature has positive effect on H radical. The hydrolysis of HNCO over an alumina catalyst made using a sol-gel process (designated as γ-Al2O3) is investigated. The conversion of HNCO is high even at the high space velocities (6×105 h-1) and low temperatures (393–673 K) in the tests with catalysts, which enhances HNCO hydrolysis and raises the ratio of NH3 to HNCO to approximately 100. The pure γ-Al2O3 shows a better catalytic performance than CuO/γ-Al2O3. The addition of CuO not only reduces the surface area but also decreases the Lewis acid sites which are recognized to have a positive effect on the catalytic activity. The apparent activation energy of the hydrolysis reaction amounts to about 25 kJ/mol in 393–473 K while 13 kJ/mol over 473 K. The overall hydrolysis reaction rate on catalysts is mainly determined by external and internal mass-transfer limitations.
文摘电催化尿素氧化(UOR)替代动力学缓慢的析氧反应(OER)为高效制氢提供了新的思路。本研究通过简单的二次水热法制备了三维Ni_(3)S_(2)/NF微球催化剂(3D-Ni_(3)S_(2)/NF),由于独特的3D结构为UOR提供了高度开放的活性区域,并加快了电荷转移速率,3D-Ni_(3)S_(2)/NF表现出明显优于1D,2D-Ni_(3)S_(2)/NF电催化氧化尿素的活性。在1 mol L^(-1)KOH+0.33 mol L^(-1)尿素电解质溶液,3D-Ni_(3)S_(2)/NF电催化尿素氧化达到100 mA cm^(-2)的电流密度的电位仅需1.38 V vs.RHE,比OER电位减少了250 mV,同时在24 h稳定性测试中表现出良好的耐久性。此外,全尿素辅助制氢只需1.66 V即可达到50 mA cm^(-2),表现出比传统电解水(1.86 V)更低的电位。
文摘电催化水分解是实现绿色制氢的理想方法之一.然而,阳极析氧反应(OER)固有的缓慢动力学和高理论电压(1.23V),使得电解水制氢的能效受到严重限制.采用理论电位更低和热力学更有利的小分子氧化反应替代OER过程,可以在降低电能耗的同时降解污染物或生成有附加值的产物,能够带来多重效益.尿素氧化反应(UOR)具有较低的理论电压(0.37V),是替代OER的潜在反应之一.然而,UOR中复杂的六电子转移严重阻碍了尿素电解的整体效率.因此,设计经济且高效的电催化剂来促进UOR固有的缓慢动力学过程非常必要.硒化镍具有电子构型多样和结构调控灵活等优点,被认为是有效的UOR催化剂.然而,UOR过程涉及催化剂表面多种反应中间体的吸附/解吸,单相催化剂要同时满足多种反应中间的吸附/解吸是一项艰巨的挑战.众所周知,非均相电催化涉及电子转移以及电催化剂表面反应物和产物的吸附和解吸.因此,催化剂的电催化性能在很大程度上取决于材料表面的电子特性.通过构建异质结构是一种有效策略,可以调节电催化剂的电子结构,优化反应中间体的化学吸附行为,实现不同组份高效协同电催化.研究表明,通过界面工程优化结构和电子特性可进一步促进UOR的动力学.MoSe_(2)具有良好的稳定性和导电性,与镍基催化剂组合构建异质结构能够改善电催化反应中的催化动力学.本文通过简单的水热和低温硒化方法构建了异质NiSe_(2)/MoSe_(2)微球作为UOR的电催化剂.差分电荷密度和Mulliken电荷分析结果表明,MoSe_(2)与NiSe_(2)的耦合引起界面处的电荷重新分布,促使电子从NiSe_(2)向MoSe_(2)转移,更容易形成高价态Ni(NiOOH)活性物种.另外,异质界面的构建优化了催化剂表面的电子结构并调节d带中心,改变反应途径,降低反应能垒,从而提高UOR的反应活性.异质结NiSe_(2)/MoSe_(2)微球由于其独特的结构特征、强的协同耦合作用、增加的活性中心和高含量的高价Ni3+物种的综合优势而具有高效的催化性能.当负载在玻碳电极上时,仅需1.33 V的电压就能驱动10 m Acm^(-2)的电流密度,该活性优于大多数已报道的非贵金属UOR催化剂.将NiSe_(2)/MoSe_(2)催化剂组装到UOR//HER电解槽中时,NiSe_(2)/MoSe_(2)|Pt/C具有较低的操作电压和长期稳定性,在1.47 V的电池电压下电流密度达到10 m Acm^(-2),比单纯的水电解降低了约220 m V.与OER相比,热力学上有利的UOR可以作为阳极OER替代反应.综上,本文为能源/环境相关的催化反应提供了一个有效的催化剂体系,对构建高效异质结催化系统具有借鉴意义.
