掺杂及电场条件下石墨烯若干催化过程的第一原理研究
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摘要
自从2004年由英国科学家发现以来，石墨烯就成为备受瞩目的研究热点。石墨烯是由sp2杂化的碳原子所组成的二维蜂窝状晶体点阵，其厚度仅为0.35nm，是世界上最薄的二维材料。这种特殊的结构使得石墨烯具有许多新奇而优异的物理性能。例如石墨烯具有超高的载流子迁移率，其常温下的载流子迁移率可达2×105cm2.V-1.s-1,远远超过商用硅片的载流子迁移率；石墨烯是已测试材料中强度最高的，其强度达到130GPa,是钢的100多倍；石墨烯还具有光学透明性和生物适应性等优异性能。因此，石墨烯在很多领域都具有重要的应用前景。
然而，目前的研究主要集中在石墨烯的光电性能上，对石墨烯表面润湿性的研究则很少见诸报端。随着智能表面概念的提出，可逆的控制石墨烯表面的润湿性就显得尤为重要。而当石墨烯应用于超级电容器的电极材料和生物支撑材料等场合时，理想的情况是石墨烯既具有亲水性，又具有导电性。另外，石墨烯超大的表面/体积比使其成为优良的异相催化支撑材料。氢气做为可再生的清洁能源引起了人们极大的研究兴趣，其在体积浓度大于4%时极易燃烧并引起爆炸，因此有必要研究高灵敏度的氢气传感器。一氧化碳氧化在清洁空气、CO2激光器净化以及去除H2中的CO防止燃料电池电极中毒等方面有着重要的应用，开发高效的CO室温氧化催化剂具有很重要的意义。本文采用第一原理计算方法，研究了电场及掺杂对石墨烯若干催化过程的影响，拓展了石墨烯的应用领域。
主要研究内容分为以下四部分：
首先，我们利用第一原理方法研究了电场下水分子在石墨烯上的分解吸附情况。结果表明负电场可以促进水分子的分解吸附，在电场F=0.39V/时水分子在石墨烯上的分解能垒消失，这使得石墨烯变为亲水性。而正电场起到相反的作用，在正电场F=0.36V/时H原子和OH基团在石墨烯上的脱吸附能垒消失，这使得石墨烯恢复为疏水性。所以，电场可以作为一个开关来控制石墨烯的润湿性。
其次，我们应用第一原理计算方法研究了铝掺杂对水分子在石墨烯上分解吸附的影响。结果表明，铝掺杂石墨烯可以极大的降低水分子在石墨烯上的分解能垒至0.413eV，进而在室温下可以自发地将石墨烯由疏水性转变为亲水性。同时，石墨烯还保持导电性。因此，铝掺杂的石墨烯可以应用于超级电容器的电极材料和生物支撑材料等场合。
再次，通过第一原理计算方法，我们研究了碳原子空位对于H2分子在石墨烯上分解吸附的影响。结果表明石墨烯上的单原子碳空位可以有效的降低H2分子分解吸附的能垒至0.805eV，然后将第二个H2分子的分解能垒降低为0.869eV。根据能带结构，H2分子分解吸附之后石墨烯的电子性能变化显著。H2分解吸附相图表明在氢气偏压极小(1035mol/L)的情况下空位处也可以分解吸附上H2分子。因此单原子空位石墨烯在氢气传感器方面有着重要的应用。
最后，我们通过第一原理方法研究了CO分子在Al掺杂石墨烯上的催化氧化过程。结果表明CO氧化过程遵循LH机制，并且速率控制步骤(CO+O2→OOCO)的反应能垒是0.32eV，远低于ER机制下的反应能垒。Hirshfeld电荷分析表明O2分子通过Al原子向CO转移电荷在CO氧化过程中起到了重要作用。因此Al掺杂的石墨烯可以成为高效的CO氧化催化剂。
Since the experimental observation in2004by the English scientists, graphenehave become the focus in many areas. Graphene, a single layer of sp2hybridizedcarbon atoms possesses two dimentional honeycomb-like lattice with thickness ofonly0.35nm. This special configuration endues graphene many excellent properties,such as elcellent electronic transport performance, ultrahigh mechanical strength,large optical transparency, high thermal conductivity and good biocompatibility. Thecharge mobility of graphene exceeds2×105cm2.V-1.s-1at room temperature, ten timeshigher than that of the conmercial silicon wafers. Also graphene possesses the largeststrength of130GPa. These characteristics have further stimulated its applications inmany important fields, such as high-performance composites, molecular electronics,field-emission devices, sensors, hydrogen storage materials and biomedicalapplications.
However, most of previous studies focused on the photoelectric performance ofgraphene, and not on its surface properties. The surface properties of graphene, whichstrongly depend on chemical composition and morphology, are highly significant inthe applications. Density Functional Theory calculations and experimentalobservations indicated that the graphene surface is highly hydrophobic. With thedevelopments of smart surface, reversible transition of graphene from hydrophobic tohydrophilic is important in the presence of external stimulation. In the applications ofelectrode materials of supercapacitors and biomaterials supports, it is desirable thatgraphene is hydrophilic and conductive since the former improves the wettingbetween graphene and polar electrolytes or biological molecules, while the latterenhances the transport of free carriers. Therefore, the development of stablehydrophilic and conductive graphene surface is essential for the above applications.
Hydrogen has attracted great interest because it is a clean and renewable energysource. Hydrogen is present widely in nuclear reactors, coal mines and semiconductormanufacturing, etc. Because hydrogen is highly flammable and explosive withvolume concentration of more than4%, developing highly sensitive hydrogen sensorsis thus important. The oxidation of carbon monoxide (CO) has attracted great interests due to its importance in applications such as cleaning air and atmosphere purificationfor CO2lasers, as well as removing CO from hydrogen gas fuel to avoid electrodepoisoning in fuel cells. Therefore, developing low cost catalysts for CO oxidation atroom temperature is desirable. Moreover, the large surface to volume ratio alsobenefits for graphene as a support for heterogeneous catalysts. Therefore, we expectthat graphene may be highly active as a catalyst for the H2sensors and CO oxidation.Base on the first principles calculations, we have investigated several catalyticprocesses on graphene in the presence of electric field and dopants.
The research contents mainly divided into four parts:
(1) Catalytic effect of a perpendicular electric field on the reversible transition ofgraphene with water from hydrophobic to hydrophilic has been investigated byusing first principles calculations. It is found that a negative electric field F canreduce the energy barrier for H2O dissociative adsorption on graphene, under F=0.39V/, the energy barrier becomes negative and the dissociativeadsorption occurs smoothly without any potential barrier, which results inhydrophilic graphene. While a positive electric field has an opposite effect, thepositive electric field of F=0.36V/leads to a negative desorption energybarrier for the desorption of H and OH from graphene, making the graphene behydrophobic again. Therefore, the electric field can act as a switch to reversiblychange the graphene from hydrophobic to hydrophilic in the presence of watervapor.
(2) The effect of Al dopant on the dissociative adsorption of a H2O molecule ongraphene is investigated by using first principles calculations. It is found thatdoping Al into graphene can facilitate the dissociative adsorption of H2Omolecules. The dissociative energy barrier is reduced to0.456eV on Al dopedgraphene and the reaction releases energy of0.413eV, which indicates asmooth dissociative adsorption on Al doped graphene at room temperature. Thedissociative adsorption of H2O molecules can convert the Al doped graphenefrom hydrophobic to hydrophilic while obtaining conductive graphene withdoping concentration higher than5.56%. The mechanism of the above is that Alcan facilitate the dissociative adsorption of H2O on graphene through mixinghybridization between its p orbit and1b1orbit of the H2O molecule. This hydrophilic and conductive graphene has potential applications insupercapacitor and biomaterial supports.
(3) To facilitate the dissociative adsorption of H2molecules on pristine graphene,mono atom vacancy is considered to be added into graphene, which leads toreduction of the dissociative energy barrier of H2molecule on graphene to0.805eV for the first H2and0.869eV for the second one by using the first principlescalculations. The electronic structure of graphene and conductivity significantlychange before and after H2adsorption. In addition, the related dissociativeadsorption phase diagrams under different temperatures and partial pressuresshow that this dissociative adsorption at room temperature is very sensitive(1035mol/L). Therefore, this defected graphene is promising for ultrasensitiveroom temperature hydrogen sensors.
(4) The oxidation of CO molecule on Al embedded graphene has been investigatedby using the first principles calculations. Two possible oxidation mechanismsEley Rideal (ER) and Langmuir Hinshelwood (LH) mechanisms are bothconsidered. In the LH mechanism, O2and CO molecules are firstly co adsorbedon Al embedded graphene, the energy barrier for the rate limiting step (CO+O2→OOCO) is only0.32eV, much lower than that of ER mechanism, whichindicates that LH mechanism is more favourable for CO oxidation onAl embedded graphene. Hirshfeld charge analysis shows that embedded Alatom would modify the charge distributions of co adsorbed O2and COmolecules. The charge transfer from O2to CO molecule through the embeddedAl atom plays an important role for the CO oxidation along the LH mechanism.Our result shows that the low cost Al embedded graphene is an efficientcatalyst for CO oxidation at room temperature.
然而，目前的研究主要集中在石墨烯的光电性能上，对石墨烯表面润湿性的研究则很少见诸报端。随着智能表面概念的提出，可逆的控制石墨烯表面的润湿性就显得尤为重要。而当石墨烯应用于超级电容器的电极材料和生物支撑材料等场合时，理想的情况是石墨烯既具有亲水性，又具有导电性。另外，石墨烯超大的表面/体积比使其成为优良的异相催化支撑材料。氢气做为可再生的清洁能源引起了人们极大的研究兴趣，其在体积浓度大于4%时极易燃烧并引起爆炸，因此有必要研究高灵敏度的氢气传感器。一氧化碳氧化在清洁空气、CO2激光器净化以及去除H2中的CO防止燃料电池电极中毒等方面有着重要的应用，开发高效的CO室温氧化催化剂具有很重要的意义。本文采用第一原理计算方法，研究了电场及掺杂对石墨烯若干催化过程的影响，拓展了石墨烯的应用领域。
主要研究内容分为以下四部分：
首先，我们利用第一原理方法研究了电场下水分子在石墨烯上的分解吸附情况。结果表明负电场可以促进水分子的分解吸附，在电场F=0.39V/时水分子在石墨烯上的分解能垒消失，这使得石墨烯变为亲水性。而正电场起到相反的作用，在正电场F=0.36V/时H原子和OH基团在石墨烯上的脱吸附能垒消失，这使得石墨烯恢复为疏水性。所以，电场可以作为一个开关来控制石墨烯的润湿性。
其次，我们应用第一原理计算方法研究了铝掺杂对水分子在石墨烯上分解吸附的影响。结果表明，铝掺杂石墨烯可以极大的降低水分子在石墨烯上的分解能垒至0.413eV，进而在室温下可以自发地将石墨烯由疏水性转变为亲水性。同时，石墨烯还保持导电性。因此，铝掺杂的石墨烯可以应用于超级电容器的电极材料和生物支撑材料等场合。
再次，通过第一原理计算方法，我们研究了碳原子空位对于H2分子在石墨烯上分解吸附的影响。结果表明石墨烯上的单原子碳空位可以有效的降低H2分子分解吸附的能垒至0.805eV，然后将第二个H2分子的分解能垒降低为0.869eV。根据能带结构，H2分子分解吸附之后石墨烯的电子性能变化显著。H2分解吸附相图表明在氢气偏压极小(1035mol/L)的情况下空位处也可以分解吸附上H2分子。因此单原子空位石墨烯在氢气传感器方面有着重要的应用。
最后，我们通过第一原理方法研究了CO分子在Al掺杂石墨烯上的催化氧化过程。结果表明CO氧化过程遵循LH机制，并且速率控制步骤(CO+O2→OOCO)的反应能垒是0.32eV，远低于ER机制下的反应能垒。Hirshfeld电荷分析表明O2分子通过Al原子向CO转移电荷在CO氧化过程中起到了重要作用。因此Al掺杂的石墨烯可以成为高效的CO氧化催化剂。
Since the experimental observation in2004by the English scientists, graphenehave become the focus in many areas. Graphene, a single layer of sp2hybridizedcarbon atoms possesses two dimentional honeycomb-like lattice with thickness ofonly0.35nm. This special configuration endues graphene many excellent properties,such as elcellent electronic transport performance, ultrahigh mechanical strength,large optical transparency, high thermal conductivity and good biocompatibility. Thecharge mobility of graphene exceeds2×105cm2.V-1.s-1at room temperature, ten timeshigher than that of the conmercial silicon wafers. Also graphene possesses the largeststrength of130GPa. These characteristics have further stimulated its applications inmany important fields, such as high-performance composites, molecular electronics,field-emission devices, sensors, hydrogen storage materials and biomedicalapplications.
However, most of previous studies focused on the photoelectric performance ofgraphene, and not on its surface properties. The surface properties of graphene, whichstrongly depend on chemical composition and morphology, are highly significant inthe applications. Density Functional Theory calculations and experimentalobservations indicated that the graphene surface is highly hydrophobic. With thedevelopments of smart surface, reversible transition of graphene from hydrophobic tohydrophilic is important in the presence of external stimulation. In the applications ofelectrode materials of supercapacitors and biomaterials supports, it is desirable thatgraphene is hydrophilic and conductive since the former improves the wettingbetween graphene and polar electrolytes or biological molecules, while the latterenhances the transport of free carriers. Therefore, the development of stablehydrophilic and conductive graphene surface is essential for the above applications.
Hydrogen has attracted great interest because it is a clean and renewable energysource. Hydrogen is present widely in nuclear reactors, coal mines and semiconductormanufacturing, etc. Because hydrogen is highly flammable and explosive withvolume concentration of more than4%, developing highly sensitive hydrogen sensorsis thus important. The oxidation of carbon monoxide (CO) has attracted great interests due to its importance in applications such as cleaning air and atmosphere purificationfor CO2lasers, as well as removing CO from hydrogen gas fuel to avoid electrodepoisoning in fuel cells. Therefore, developing low cost catalysts for CO oxidation atroom temperature is desirable. Moreover, the large surface to volume ratio alsobenefits for graphene as a support for heterogeneous catalysts. Therefore, we expectthat graphene may be highly active as a catalyst for the H2sensors and CO oxidation.Base on the first principles calculations, we have investigated several catalyticprocesses on graphene in the presence of electric field and dopants.
The research contents mainly divided into four parts:
(1) Catalytic effect of a perpendicular electric field on the reversible transition ofgraphene with water from hydrophobic to hydrophilic has been investigated byusing first principles calculations. It is found that a negative electric field F canreduce the energy barrier for H2O dissociative adsorption on graphene, under F=0.39V/, the energy barrier becomes negative and the dissociativeadsorption occurs smoothly without any potential barrier, which results inhydrophilic graphene. While a positive electric field has an opposite effect, thepositive electric field of F=0.36V/leads to a negative desorption energybarrier for the desorption of H and OH from graphene, making the graphene behydrophobic again. Therefore, the electric field can act as a switch to reversiblychange the graphene from hydrophobic to hydrophilic in the presence of watervapor.
(2) The effect of Al dopant on the dissociative adsorption of a H2O molecule ongraphene is investigated by using first principles calculations. It is found thatdoping Al into graphene can facilitate the dissociative adsorption of H2Omolecules. The dissociative energy barrier is reduced to0.456eV on Al dopedgraphene and the reaction releases energy of0.413eV, which indicates asmooth dissociative adsorption on Al doped graphene at room temperature. Thedissociative adsorption of H2O molecules can convert the Al doped graphenefrom hydrophobic to hydrophilic while obtaining conductive graphene withdoping concentration higher than5.56%. The mechanism of the above is that Alcan facilitate the dissociative adsorption of H2O on graphene through mixinghybridization between its p orbit and1b1orbit of the H2O molecule. This hydrophilic and conductive graphene has potential applications insupercapacitor and biomaterial supports.
(3) To facilitate the dissociative adsorption of H2molecules on pristine graphene,mono atom vacancy is considered to be added into graphene, which leads toreduction of the dissociative energy barrier of H2molecule on graphene to0.805eV for the first H2and0.869eV for the second one by using the first principlescalculations. The electronic structure of graphene and conductivity significantlychange before and after H2adsorption. In addition, the related dissociativeadsorption phase diagrams under different temperatures and partial pressuresshow that this dissociative adsorption at room temperature is very sensitive(1035mol/L). Therefore, this defected graphene is promising for ultrasensitiveroom temperature hydrogen sensors.
(4) The oxidation of CO molecule on Al embedded graphene has been investigatedby using the first principles calculations. Two possible oxidation mechanismsEley Rideal (ER) and Langmuir Hinshelwood (LH) mechanisms are bothconsidered. In the LH mechanism, O2and CO molecules are firstly co adsorbedon Al embedded graphene, the energy barrier for the rate limiting step (CO+O2→OOCO) is only0.32eV, much lower than that of ER mechanism, whichindicates that LH mechanism is more favourable for CO oxidation onAl embedded graphene. Hirshfeld charge analysis shows that embedded Alatom would modify the charge distributions of co adsorbed O2and COmolecules. The charge transfer from O2to CO molecule through the embeddedAl atom plays an important role for the CO oxidation along the LH mechanism.Our result shows that the low cost Al embedded graphene is an efficientcatalyst for CO oxidation at room temperature.
引文
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