CN115920945B - A hydroxylated graphite phase carbon nitride photocatalyst and its preparation method and application - Google Patents
A hydroxylated graphite phase carbon nitride photocatalyst and its preparation method and application Download PDFInfo
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Abstract
本发明属于纳米光催化材料技术领域，具体涉及一种羟基化石墨相氮化碳光催化剂及其制备方法与应用。本发明采用乙醇和甘油对石墨相氮化碳g‑C3N4进行表面羟基化改性，通过此方法得到的g‑C3N4‑OH表现出更大的比表面积，其中的羟基可以促进光生电子传输与分离，提高光生电荷的利用效率，更重要的是羟基能够降低g‑C3N4表面的氧化还原反应能垒，从而有利于实现光催化分解水产氢，相比于g‑C3N4光催化剂，所述g‑C3N4‑OH光催化剂具有更高效的光催化分解海水制氢活性。并且所述制备方法简单，可操作性强，重复性好，能进行放大生产，具有良好的应用前景。
The present invention belongs to the technical field of nano-photocatalytic materials, and specifically relates to a hydroxylated graphite phase carbon nitride photocatalyst and its preparation method and application. The present invention adopts ethanol and glycerol to carry out surface hydroxylation modification on graphite phase carbon nitride g-C 3 N 4 , and the g-C 3 N 4 ‑OH obtained by this method shows a larger specific surface area, wherein the hydroxyl group can promote the transmission and separation of photogenerated electrons, improve the utilization efficiency of photogenerated charges, and more importantly, the hydroxyl group can reduce the redox reaction energy barrier on the surface of g-C 3 N 4 , so as to facilitate the realization of photocatalytic decomposition of water to produce hydrogen, and compared with g-C 3 N 4 photocatalyst, the g-C 3 N 4 ‑OH photocatalyst has a more efficient photocatalytic decomposition of seawater to produce hydrogen activity. And the preparation method is simple, highly operable, and has good repeatability, can be scaled up for production, and has good application prospects.
Description
技术领域Technical Field
本发明属于纳米光催化材料技术领域，更具体地，涉及一种羟基化石墨相氮化碳光催化剂及其制备方法与应用。The present invention belongs to the technical field of nano photocatalytic materials, and more specifically, relates to a hydroxylated graphite phase carbon nitride photocatalyst and a preparation method and application thereof.
背景技术Background Art
化石燃料的短缺和环境污染的问题日益严峻，引起了人们的关注，人们着力于开发新型的无污染的可持续的能源。由于氢气具有高能量密度和环境友好型的特点，使其在取代化石燃料能源方面展示出巨大的潜力。当前的储氢材料主要包括：含氢的化合物(如：NaBH4、水合肼、有机含氢化合物)和水，这些都是获得氢气的源头。氢能作为一种二次能源，需要通过制氢技术进行提取。根据氢能生产来源和生产过程中的排放情况，人们将氢能分别冠以灰氢、蓝氢、绿氢之称。其中，灰氢是通过化石燃料燃烧产生的氢气，在生产过程中会有二氧化碳等的排放，其产量约占当今全球氢气产量的95％；蓝氢由煤或天然气等化石燃料制得，在蓝氢的制备过程中将二氧化碳副产品捕获、利用和封存((Carbon Capture，Utilization and Storage，简称CCUS)，从而实现碳中和；其中的天然气和煤虽然也属于化石燃料，在生产蓝氢时也会产生温室气体，但由于使用了CCUS等先进技术，温室气体被捕获，减轻了对地球环境的影响，实现了低排放生产；绿氢是指利用可再生能源分解水得到的氢气，其燃烧时只产生水，从源头上实现了二氧化碳零排放，是纯正的绿色新能源，在全球能源转型中扮演着重要角色。而利用光催化技术分解水，不会产生任何的污染气体或者温室气体，通过此途径获得的氢气为真正的绿色能源。并且，氢气能够成为给设备提供动力的化石能源的最佳代替者。The shortage of fossil fuels and the increasingly serious problems of environmental pollution have attracted people's attention. People are working hard to develop new pollution-free and sustainable energy. Due to its high energy density and environmental friendliness, hydrogen has great potential in replacing fossil fuel energy. Current hydrogen storage materials mainly include: hydrogen-containing compounds (such as: NaBH4 , hydrazine hydrate, organic hydrogen-containing compounds) and water, which are the sources of hydrogen. Hydrogen energy, as a secondary energy source, needs to be extracted through hydrogen production technology. According to the source of hydrogen energy production and the emissions during the production process, people call hydrogen energy gray hydrogen, blue hydrogen, and green hydrogen. Among them, gray hydrogen is hydrogen produced by burning fossil fuels. During the production process, carbon dioxide and other gases will be emitted. Its output accounts for about 95% of the global hydrogen production today. Blue hydrogen is produced from fossil fuels such as coal or natural gas. During the preparation of blue hydrogen, the carbon dioxide byproduct is captured, utilized and stored (Carbon Capture, Utilization and Storage, referred to as CCUS), thereby achieving carbon neutrality. Although natural gas and coal are also fossil fuels and will produce greenhouse gases when producing blue hydrogen, due to the use of advanced technologies such as CCUS, greenhouse gases are captured, reducing the impact on the earth's environment and achieving low-emission production. Green hydrogen refers to hydrogen obtained by decomposing water using renewable energy. When it burns, it only produces water, achieving zero carbon dioxide emissions from the source. It is a pure green new energy and plays an important role in the global energy transformation. The decomposition of water using photocatalytic technology does not produce any polluting gases or greenhouse gases. The hydrogen obtained in this way is a truly green energy. In addition, hydrogen can be the best substitute for fossil energy to power equipment.
早在1972年Fujishima和Honda发现了n-型半导体TiO2光电催化水分解产氢(Electrochemical photolysis of water at a semiconductor electrode，Nature，1972，238,37-38)，可以利用太阳能实现半导体基的光催化产氢，并且该策略已经被认为是解决当前世界能源问题最有效的方法。该策略实施的关键是发展具有高效稳定光催化性能的光催化剂。As early as 1972, Fujishima and Honda discovered the photocatalytic decomposition of water to produce hydrogen by n-type semiconductor TiO 2 (Electrochemical photolysis of water at a semiconductor electrode, Nature, 1972, 238, 37-38). Semiconductor-based photocatalytic hydrogen production can be achieved using solar energy, and this strategy has been considered to be the most effective way to solve the current world energy problem. The key to the implementation of this strategy is to develop photocatalysts with efficient and stable photocatalytic performance.
在光催化剂中，石墨相氮化碳(g-C3N4)光催化剂具有合适的能带位置、化学稳定性和良好的可见光响应范围等优点，被广泛用于光催化转化领域；但体相的g-C3N4存在表面积较小和光生电子-空穴对的快速复合等不足，以上这些严重限制了它的实际应用。许多研究者一直致力于寻找有效的方法来改性g-C3N4，比如：多步热缩聚处理(Enhancing visible-light hydrogen evolution performance of crystalline carbon nitride by defectengineering,ChemSusChem,2019,12，3257-3262)、热缩聚不同的富N前驱体(Synthesis ofgraphitic carbon nitride via direct polymerization using different precursorsand its application in lithium–sulfur batteries,Appl.Phy.A Mater.,2018,124，758)、元素掺杂(Photoelectrochemical and EPR features of polymeric C3N4 and O-modified C3N4 employed for selective photocatalytic oxidation of alcohols toaldehydes,Catal.Today,2019,328，21-28)和形貌调控(Phosphorus-doped carbonnitride tubes with a layered micro-nanostructure for enhanced visible-lightphotocatalytic hydrogen evolution,Angew.Chem.Int.Ed.,2016,55，1830-1834)等。可见，多孔g-C3N4可以增加比表面积、缩短光生载流子传输距离，但是g-C3N4光催化剂和反应物之间的亲和力却一直被忽略，尤其是光生载流子分离效率低的瓶颈也一直未被解决。Among photocatalysts, graphite carbon nitride (gC 3 N 4 ) photocatalyst has the advantages of suitable energy band position, chemical stability and good visible light response range, and is widely used in the field of photocatalytic conversion; however, the bulk phase of gC 3 N 4 has shortcomings such as small surface area and rapid recombination of photogenerated electron-hole pairs, which seriously limit its practical application. Many researchers have been committed to finding effective methods to modify g-C 3 N 4 , such as: multi-step thermal polycondensation treatment (Enhancing visible-light hydrogen evolution performance of crystalline carbon nitride by defect engineering, ChemSusChem, 2019, 12, 3257-3262), thermal polycondensation of different N-rich precursors (Synthesis of graphitic carbon nitride via direct polymerization using different precursors and its application in lithium–sulfur batteries, Appl. Phy. A Mater., 2018, 124, 758), element doping (Photoelectrochemical and EPR features of polymeric C 3 N 4 and O-modified C 3 N 4 employed for selective photocatalytic oxidation of alcohols toaldehydes, Catal. Today, 2019, 328, 21-28) and morphology control (Phosphorus-doped carbon nitride tubes with a layered micro-nanostructure for enhanced visible-light photocatalytic hydrogen evolution, Angew. Chem. Int. Ed., 2016, 55, 1830-1834), etc. It can be seen that porous g-C 3 N 4 can increase the specific surface area and shorten the transmission distance of photogenerated carriers, but the affinity between g-C 3 N 4 photocatalyst and reactants has been ignored, especially the bottleneck of low efficiency of photogenerated carrier separation has not been solved.
发明内容Summary of the invention
本发明要解决的技术问题是克服现有g-C3N4光催化剂的光生载流子分离效率低、表面氧化还原反应动力学缓慢、光催化效率低的缺陷和不足，提供一种富羟基化、多孔、高比表面积、低光生电荷复合效率、低成本和高催化活性的石墨相氮化碳光催化剂(g-C3N4-OH)的制备方法。The technical problem to be solved by the present invention is to overcome the defects and shortcomings of the existing gC 3 N 4 photocatalyst, such as low photogenerated carrier separation efficiency, slow surface redox reaction kinetics and low photocatalytic efficiency, and to provide a method for preparing a graphite phase carbon nitride photocatalyst (gC 3 N 4 -OH) which is rich in hydroxylation, porous, has a high specific surface area, has low photogenerated charge recombination efficiency, is low in cost and has high catalytic activity.
本发明的目的是提供所述制备方法制备得到的g-C3N4-OH。The purpose of the present invention is to provide gC 3 N 4 -OH prepared by the preparation method.
本发明另一目的是提供所述g-C3N4-OH在光催化分解水制氢中的应用。Another object of the present invention is to provide the use of the gC 3 N 4 —OH in photocatalytic water decomposition to produce hydrogen.
本发明上述目的通过以下技术方案实现：The above-mentioned purpose of the present invention is achieved through the following technical solutions:
一种g-C3N4-OH光催化剂的制备方法，包括如下步骤：A method for preparing a gC 3 N 4 -OH photocatalyst comprises the following steps:
将g-C3N4纳米片分散在乙醇和甘油中，于160～200℃溶剂热反应完全，后处理，即得。The gC 3 N 4 nanosheets are dispersed in ethanol and glycerol, and the solvent thermal reaction is completed at 160-200° C., and then post-treated to obtain the product.
本发明利用乙醇和甘油使g-C3N4表面极化，得到的g-C3N4-OH不仅表现出来更大的比表面积，而且其中的羟基(-OH)能在表面区域形成诱导电场，并抬高能带间隙边，从而提高电荷分离效率。此外，-OH的存在还促进水的氧化反应的动力学过程，因此，与普通g-C3N4相比，g-C3N4-OH中的光生电荷分离效率高，表面氧化能力强，表现出增强的光催化分解水产氢活性。The present invention utilizes ethanol and glycerol to polarize the surface of gC 3 N 4 , and the obtained gC 3 N 4 -OH not only exhibits a larger specific surface area, but also the hydroxyl group (-OH) therein can form an induced electric field in the surface area and raise the edge of the energy band gap, thereby improving the charge separation efficiency. In addition, the presence of -OH also promotes the kinetic process of the water oxidation reaction. Therefore, compared with ordinary gC 3 N 4 , the photogenerated charge separation efficiency in gC 3 N 4 -OH is high, the surface oxidation ability is strong, and the enhanced photocatalytic water decomposition hydrogen production activity is exhibited.
优选地，所述乙醇和甘油的体积比为3:1～1:3。Preferably, the volume ratio of ethanol to glycerol is 3:1 to 1:3.
优选地，所述溶剂热反应完全的时间为2～48h。Preferably, the solvent thermal reaction takes 2 to 48 hours to complete.
进一步地，所述g-C3N4纳米片为常规方法制备得到或通过购买得到。Furthermore, the gC 3 N 4 nanosheets are prepared by conventional methods or purchased.
优选地，所述g-C3N4纳米片为将尿素于450～560℃煅烧2～5h得到。Preferably, the gC 3 N 4 nanosheets are obtained by calcining urea at 450 to 560° C. for 2 to 5 hours.
更优选地，所述g-C3N4纳米片为将尿素于550℃煅烧2h得到。More preferably, the gC 3 N 4 nanosheets are obtained by calcining urea at 550° C. for 2 h.
进一步地，所述后处理包括冷却、离心、洗涤和干燥。Furthermore, the post-treatment includes cooling, centrifugation, washing and drying.
更进一步地，所述干燥为冷冻干燥。Furthermore, the drying is freeze-drying.
具体地，所述后处理的操作为将反应完全得到的物质自然降温到室温，进行离心后，用去离子水彻底清洗，进行冷冻干燥，所得即为g-C3N4-OH。Specifically, the post-treatment operation is to cool the substance obtained after the reaction to room temperature naturally, centrifuge it, wash it thoroughly with deionized water, and freeze-dry it to obtain gC 3 N 4 -OH.
本发明还提供所述制备方法制备得到的g-C3N4-OH。The present invention also provides gC 3 N 4 -OH prepared by the preparation method.
另外的，本发明还提供所述g-C3N4-OH在光催化水制氢中的应用。g-C3N4-OH在催化水制氢过程中涉及到水分子在催化剂表面的吸附-解离过程，g-C3N4-OH表面具有大量的的羟基，而羟基具有亲水性，有利于水分子在表面的吸附，促进水分解制氢进程。In addition, the present invention also provides the use of gC 3 N 4 -OH in photocatalytic water hydrogen production. The process of gC 3 N 4 -OH catalyzing water hydrogen production involves the adsorption-dissociation process of water molecules on the catalyst surface. The surface of gC 3 N 4 -OH has a large number of hydroxyl groups, which are hydrophilic and are conducive to the adsorption of water molecules on the surface, thereby promoting the process of water decomposition and hydrogen production.
进一步地，所述光催化制氢需要加入Pt金属催化剂作为助催化剂。Furthermore, the photocatalytic hydrogen production requires the addition of a Pt metal catalyst as a co-catalyst.
优选地，所述Pt金属催化剂包括氯铂酸、二氯化铂和硝酸铂。在光催化过程中，g-C3N4-OH吸收光，产生还原性的光电子，光电子还原Pt金属催化剂中的铂离子，形成g-C3N4-O-Pt复合光催化剂，Pt原子作为光催化水分解产氢的活性位点。而传统的Pt改性的g-C3N4复合光催化剂的结构是Pt纳米颗粒负载在g-C3N4的表面，参与反应的Pt纳米颗粒。Preferably, the Pt metal catalyst includes chloroplatinic acid, platinum dichloride and platinum nitrate. In the photocatalytic process, gC 3 N 4 -OH absorbs light to generate reducing photoelectrons, which reduce the platinum ions in the Pt metal catalyst to form a gC 3 N 4 -O-Pt composite photocatalyst, and the Pt atoms serve as active sites for photocatalytic water decomposition and hydrogen production. The structure of the traditional Pt-modified gC 3 N 4 composite photocatalyst is that Pt nanoparticles are loaded on the surface of gC 3 N 4 , and the Pt nanoparticles participating in the reaction.
更优选地，所述Pt金属催化剂为氯铂酸。More preferably, the Pt metal catalyst is chloroplatinic acid.
本发明具有以下有益效果：本发明采用乙醇和甘油对g-C3N4进行表面羟基化改性，通过此方法得到的g-C3N4-OH光催化剂表现出更大的比表面积，其中的羟基(-OH)可以促进光生电子传输与分离，提高光生电荷的利用效率，更重要的是羟基能够降低g-C3N4表面的氧化还原反应能垒，从而有利于实现光催化分解水产氢，相比于g-C3N4光催化剂，所述g-C3N4-OH光催化剂具有更高效的光催化分解海水制氢活性。并且所述制备方法简单，可操作性强，重复性好，能进行放大生产，具有良好的应用前景。The invention has the following beneficial effects: the invention uses ethanol and glycerol to perform surface hydroxylation modification on gC 3 N 4 , and the gC 3 N 4 -OH photocatalyst obtained by the method exhibits a larger specific surface area, wherein the hydroxyl group (-OH) can promote the transmission and separation of photogenerated electrons, and improve the utilization efficiency of photogenerated charges, and more importantly, the hydroxyl group can reduce the redox reaction energy barrier on the surface of gC 3 N 4 , thereby facilitating the photocatalytic decomposition of water to produce hydrogen, and compared with the gC 3 N 4 photocatalyst, the gC 3 N 4 -OH photocatalyst has a more efficient photocatalytic decomposition of seawater to produce hydrogen activity. In addition, the preparation method is simple, highly operable, and has good repeatability, and can be scaled up for production, and has good application prospects.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1是对比例1制备的g-C3N4和实施例1制备的g-C3N4-OH的XRD图谱。FIG. 1 is an XRD spectrum of gC 3 N 4 prepared in Comparative Example 1 and gC 3 N 4 -OH prepared in Example 1. FIG.
图2是对比例1制备的g-C3N4的SEM图。FIG. 2 is a SEM image of gC 3 N 4 prepared in Comparative Example 1.
图3是实施例3制备的g-C3N4-OH的SEM图。FIG3 is a SEM image of gC 3 N 4 —OH prepared in Example 3.
图4是对比例1制备的g-C3N4和实施例2制备的g-C3N4-OH的红外光谱图谱。FIG. 4 is an infrared spectrum of gC 3 N 4 prepared in Comparative Example 1 and gC 3 N 4 -OH prepared in Example 2. FIG.
图5是对比例1制备的g-C3N4和实施例1制备的g-C3N4-OH的荧光发射光谱图。FIG5 is a fluorescence emission spectra of gC 3 N 4 prepared in Comparative Example 1 and gC 3 N 4 -OH prepared in Example 1. FIG.
图6是对比例1制备的g-C3N4和实施例3制备的g-C3N4-OH的光电流响应曲线图。FIG6 is a photocurrent response curve diagram of gC 3 N 4 prepared in Comparative Example 1 and gC 3 N 4 -OH prepared in Example 3.
图7是对比例1制备的g-C3N4和实施例2制备的g-C3N4-OH的电催化析氢极化曲线图。FIG. 7 is a graph showing polarization curves of electrocatalytic hydrogen evolution of gC 3 N 4 prepared in Comparative Example 1 and gC 3 N 4 -OH prepared in Example 2.
图8是对比例1制备的g-C3N4和实施例1、2和3分别制备的g-C3N4-OH的光催化剂的产氢总量随光照时间积累曲线图。FIG8 is a graph showing the accumulation of the total amount of hydrogen produced by the photocatalysts of gC 3 N 4 prepared in Comparative Example 1 and gC 3 N 4 -OH prepared in Examples 1, 2 and 3 as a function of illumination time.
具体实施方式DETAILED DESCRIPTION
以下结合说明书附图和具体实施例来进一步说明本发明，但实施例并不对本发明做任何形式的限定。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。The present invention is further described below in conjunction with the accompanying drawings and specific examples, but the examples do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.
除非特别说明，以下实施例所用试剂和材料均为市购。Unless otherwise specified, the reagents and materials used in the following examples are commercially available.
光催化剂的表征与性能测试的具体测试方法参考如下步骤:The specific test methods for characterization and performance testing of photocatalysts refer to the following steps:
(1)扫描电子显微镜(SEM)分析所用的仪器为日本电子公司的JSM-6700F型扫描式电子显微镜观察试样表面的微观形貌，用导电胶将样品固定在样品台上，镀金处理后直接观察，加速电压2～20kV。(1) Scanning electron microscope (SEM) analysis The instrument used was a JSM-6700F scanning electron microscope from JEOL Ltd. to observe the microscopic morphology of the sample surface. The sample was fixed on the sample stage with conductive glue and directly observed after gold plating. The acceleration voltage was 2 to 20 kV.
(2)光致荧光发光光谱(PL)所用仪器为岛津RF-6000荧光分光光度计，将粉末样品压片到平行的两块石英玻璃之间，放置到载样台上。设置激发波长为380nm，扫描波长范围为400～800nm。(2) Photoluminescence spectroscopy (PL) The instrument used was a Shimadzu RF-6000 fluorescence spectrophotometer. The powder sample was pressed between two parallel pieces of quartz glass and placed on the sample stage. The excitation wavelength was set to 380 nm and the scanning wavelength range was 400-800 nm.
(3)XRD分析所用的仪器为理学Rigaku Ultima IV型X射线衍射仪(XRD)表征所制备最终产物的晶相结构材料。测试条件为Cu靶，Kα辐射，40kV，40mA，步宽0.02°，扫描范围10～80°。样品为粉末置于样品台凹槽压平，直接检测。(3) XRD analysis The instrument used was Rigaku Ultima IV X-ray diffractometer (XRD) to characterize the crystal phase structure of the final product. The test conditions were Cu target, Kα radiation, 40 kV, 40 mA, step width 0.02°, and scanning range 10-80°. The sample was placed in the sample stage groove and flattened for direct detection.
(4)工作电极制备：将10μL的Nafion(5wt％)溶液与5.0mg的光催化剂加入到1.0mL乙醇中，超声分散得到悬浮液。取100μL悬浮液滴涂在FTO导电玻璃衬底上(2×1cm2)，自然干燥后，氩气气氛下150℃退火60min得到工作电极。(4) Preparation of working electrode: 10 μL of Nafion (5 wt%) solution and 5.0 mg of photocatalyst were added to 1.0 mL of ethanol and ultrasonically dispersed to obtain a suspension. 100 μL of the suspension was drop-coated on a FTO conductive glass substrate (2×1 cm 2 ), dried naturally, and annealed at 150° C. for 60 min in an argon atmosphere to obtain a working electrode.
(5)光电化学测试在装配有三电极***的电化学工作站(CHI 650E)上进行，铂电极与Ag/AgCl(饱和KCl)电极分别作为对电极与参比电极。用0.5M的Na2SO4溶液作为电解液。以300W氙灯作为光源，记录偏压下的瞬态光电流曲线(i-t)。以扫描速率5mV·s-1在Na2SO4溶液中测试电催化析氢反应(HER)的极化曲线。(5) Photoelectrochemical tests were performed on an electrochemical workstation (CHI 650E) equipped with a three-electrode system. A platinum electrode and an Ag/AgCl (saturated KCl) electrode were used as the counter electrode and the reference electrode, respectively. A 0.5 M Na 2 SO 4 solution was used as the electrolyte. A 300 W xenon lamp was used as the light source, and the transient photocurrent curve (it) under bias was recorded. The polarization curve of the electrocatalytic hydrogen evolution reaction (HER) was tested in Na 2 SO 4 solution at a scan rate of 5 mV·s -1 .
(6)光催化分解水反应在Labsolar 6A光催化反应***(北京泊菲莱)中进行，整个***可以与真空泵联通。将20mg光催化剂加入到装有100mL海水的反应器中，超声分散3min，然后加入0.5mg氯铂酸，搅拌均匀。将反应器与***连接并密封好，整个***用真空泵抽真空到2.0kPa，反应器用15℃的冷凝水保持恒温，反应器中的悬浮液用磁力搅拌保持悬浮。反应器为顶照式，300W氙灯作为光源，输入电压为220V，电流为15A。反应开始后，通过自动进样***每60min取一个样，送入在线气相色谱仪检测反应生成的H2。(6) The photocatalytic water splitting reaction was carried out in a Labsolar 6A photocatalytic reaction system (Beijing Bofeilai), and the entire system could be connected to a vacuum pump. 20 mg of photocatalyst was added to a reactor containing 100 mL of seawater, ultrasonically dispersed for 3 min, and then 0.5 mg of chloroplatinic acid was added and stirred evenly. The reactor was connected to the system and sealed, and the entire system was evacuated to 2.0 kPa with a vacuum pump. The reactor was kept at a constant temperature with condensed water at 15°C, and the suspension in the reactor was kept suspended with magnetic stirring. The reactor was top-illuminated, with a 300W xenon lamp as the light source, an input voltage of 220 V, and a current of 15 A. After the reaction started, a sample was taken every 60 min through the automatic sampling system and sent to an online gas chromatograph to detect the H 2 generated by the reaction.
实施例1一种g-C3N4-OH光催化剂的制备方法Example 1 A method for preparing gC 3 N 4 -OH photocatalyst
一种g-C3N4-OH光催化剂的制备方法，包括如下步骤：A method for preparing a gC 3 N 4 -OH photocatalyst comprises the following steps:
将50.0g尿素加入到体积为100mL的有盖坩埚中，在马弗炉中550℃反应2h得到了g-C3N4纳米片。将0.5g g-C3N4纳米片分散在含30mL乙醇和10mL甘油的特氟龙不锈钢高压釜中，180℃溶剂热处理4h，自然降温到室温，离心，然后用去离子水彻底清洗，进行冷冻干燥，最终得到g-C3N4-OH。50.0 g of urea was added to a 100 mL covered crucible and reacted at 550 °C for 2 h in a muffle furnace to obtain gC 3 N 4 nanosheets. 0.5 g of gC 3 N 4 nanosheets was dispersed in a Teflon stainless steel autoclave containing 30 mL of ethanol and 10 mL of glycerol, and subjected to solvent thermal treatment at 180 °C for 4 h, cooled naturally to room temperature, centrifuged, and then thoroughly washed with deionized water and freeze-dried to finally obtain gC 3 N 4 -OH.
实施例2一种g-C3N4-OH光催化剂的制备方法Example 2 A method for preparing gC 3 N 4 -OH photocatalyst
一种g-C3N4-OH光催化剂的制备方法，包括如下步骤：A method for preparing a gC 3 N 4 -OH photocatalyst comprises the following steps:
将50.0g尿素加入到体积为100mL的有盖坩埚中，在马弗炉中550℃反应2h得到了g-C3N4纳米片。将0.5g g-C3N4纳米片分散在含30mL乙醇和10mL甘油的特氟龙不锈钢高压釜中，160℃溶剂热处理4h，自然降温到室温，离心，然后用去离子水彻底清洗，进行冷冻干燥，最终得到g-C3N4-OH。50.0 g of urea was added to a 100 mL covered crucible and reacted at 550 °C for 2 h in a muffle furnace to obtain gC 3 N 4 nanosheets. 0.5 g of gC 3 N 4 nanosheets was dispersed in a Teflon stainless steel autoclave containing 30 mL of ethanol and 10 mL of glycerol, and subjected to solvent thermal treatment at 160 °C for 4 h, cooled naturally to room temperature, centrifuged, and then thoroughly washed with deionized water and freeze-dried to finally obtain gC 3 N 4 -OH.
实施例3一种g-C3N4-OH光催化剂的制备方法Example 3 Preparation method of gC 3 N 4 -OH photocatalyst
一种g-C3N4-OH光催化剂的制备方法，包括如下步骤：A method for preparing a gC 3 N 4 -OH photocatalyst comprises the following steps:
将50.0g尿素加入到体积为100mL的有盖坩埚中，在马弗炉中550℃反应2h得到了g-C3N4纳米片。将0.5g g-C3N4纳米片分散在含30mL乙醇和10mL甘油的特氟龙不锈钢高压釜中，180℃溶剂热处理20h，自然降温到室温，离心，然后用去离子水彻底清洗，进行冷冻干燥，最终得到g-C3N4-OH。50.0 g of urea was added to a 100 mL covered crucible and reacted at 550 °C for 2 h in a muffle furnace to obtain gC 3 N 4 nanosheets. 0.5 g of gC 3 N 4 nanosheets was dispersed in a Teflon stainless steel autoclave containing 30 mL of ethanol and 10 mL of glycerol, and subjected to solvent thermal treatment at 180 °C for 20 h, cooled naturally to room temperature, centrifuged, and then thoroughly washed with deionized water and freeze-dried to finally obtain gC 3 N 4 -OH.
实施例4一种g-C3N4-OH光催化剂的制备方法Example 4 A method for preparing gC 3 N 4 -OH photocatalyst
一种g-C3N4-OH光催化剂的制备方法，包括如下步骤：A method for preparing a gC 3 N 4 -OH photocatalyst comprises the following steps:
将50.0g尿素加入到体积为100mL的有盖坩埚中，在马弗炉中550℃反应2h得到了g-C3N4纳米片。将0.5g g-C3N4纳米片分散在含10mL乙醇和30mL甘油的特氟龙不锈钢高压釜中，200℃溶剂热处理2h，自然降温到室温，离心，然后用去离子水彻底清洗，进行冷冻干燥，最终得到g-C3N4-OH。50.0 g of urea was added to a 100 mL covered crucible and reacted at 550 °C for 2 h in a muffle furnace to obtain gC 3 N 4 nanosheets. 0.5 g of gC 3 N 4 nanosheets was dispersed in a Teflon stainless steel autoclave containing 10 mL of ethanol and 30 mL of glycerol, and subjected to solvent thermal treatment at 200 °C for 2 h, cooled naturally to room temperature, centrifuged, and then thoroughly washed with deionized water and freeze-dried to finally obtain gC 3 N 4 -OH.
实施例5一种g-C3N4-OH光催化剂的制备方法Example 5 A method for preparing gC 3 N 4 -OH photocatalyst
一种g-C3N4-OH光催化剂的制备方法，包括如下步骤：A method for preparing a gC 3 N 4 -OH photocatalyst comprises the following steps:
将50.0g尿素加入到体积为100mL的有盖坩埚中，在马弗炉中550℃反应2h得到了g-C3N4纳米片。将0.5g g-C3N4纳米片分散在含20mL乙醇和20mL甘油的特氟龙不锈钢高压釜中，160℃溶剂热处理48h，自然降温到室温，离心，然后用去离子水彻底清洗，进行冷冻干燥，最终得到g-C3N4-OH。50.0 g of urea was added to a 100 mL covered crucible and reacted at 550 °C for 2 h in a muffle furnace to obtain gC 3 N 4 nanosheets. 0.5 g of gC 3 N 4 nanosheets was dispersed in a Teflon stainless steel autoclave containing 20 mL of ethanol and 20 mL of glycerol, and subjected to solvent thermal treatment at 160 °C for 48 h, cooled naturally to room temperature, centrifuged, and then thoroughly washed with deionized water and freeze-dried to finally obtain gC 3 N 4 -OH.
对比例1一种g-C3N4光催化剂的制备方法Comparative Example 1: Preparation method of gC 3 N 4 photocatalyst
一种g-C3N4光催化剂的制备方法，包括如下步骤：A method for preparing a gC 3 N 4 photocatalyst comprises the following steps:
将50.0g尿素加入到体积为100mL的有盖坩埚中，在马弗炉中550℃反应2h得到了g-C3N4纳米片。50.0 g of urea was added into a covered crucible with a volume of 100 mL and reacted at 550° C. for 2 h in a muffle furnace to obtain gC 3 N 4 nanosheets.
实验例光催化剂的表征与性能测试Experimental Example Characterization and Performance Testing of Photocatalyst
测定对比例1制备的g-C3N4和实施例1制备的g-C3N4-OH的XRD图谱，结果如图1所示，g-C3N4的XRD数据显示两个位置分别位于13.3°与27.6°的强衍射峰，其分别对应于g-C3N4的(111)与(002)晶面。进行溶剂热处理后，g-C3N4-OH的XRD图谱与g-C3N4的XRD图谱相比没有明显的变化，说明溶剂热处理过程不改变g-C3N4的晶体结构。实施例2～5制备得到的g-C3N4-OH具有与实施例1基本一致的XRD图谱。The XRD patterns of gC 3 N 4 prepared in Comparative Example 1 and gC 3 N 4 -OH prepared in Example 1 were measured, and the results are shown in FIG1 . The XRD data of gC 3 N 4 show two strong diffraction peaks located at 13.3° and 27.6°, which correspond to the (111) and (002) crystal planes of gC 3 N 4 , respectively. After the solvent thermal treatment, the XRD pattern of gC 3 N 4 -OH has no obvious change compared with the XRD pattern of gC 3 N 4 , indicating that the solvent thermal treatment process does not change the crystal structure of gC 3 N 4. The gC 3 N 4 -OH prepared in Examples 2 to 5 has an XRD pattern that is substantially consistent with that of Example 1.
测定对比例1制备的g-C3N4和实施例3制备的g-C3N4-OH的SEM图，结果分别如图2和图3所示，明显地，所得g-C3N4呈纳米片状，其表面比较光滑，而g-C3N4-OH也呈纳米片状，但是其表面与g-C3N4相比略微粗糙，具有更多细小的孔，从而具有更大的比表面积。实施例1、2、4和5制备得到的g-C3N4-OH具有与实施例3基本一致的SEM形貌。The SEM images of gC 3 N 4 prepared in Comparative Example 1 and gC 3 N 4 -OH prepared in Example 3 were measured, and the results are shown in Figures 2 and 3, respectively. Obviously, the obtained gC 3 N 4 is in the form of nanosheets, and its surface is relatively smooth, while gC 3 N 4 -OH is also in the form of nanosheets, but its surface is slightly rougher than that of gC 3 N 4 , and has more fine pores, so it has a larger specific surface area. The gC 3 N 4 -OH prepared in Examples 1, 2, 4 and 5 has a SEM morphology that is basically consistent with that of Example 3.
测定对比例1制备的g-C3N4和实施例2制备的g-C3N4-OH的红外光谱图谱，结果如图4所示，与g-C3N4相比，g-C3N4-OH在3325cm-1处的羟基特征峰的强度更高，说明溶剂热过程使得g-C3N4-OH的表面接枝了羟基。实施例1、3、4和5制备得到的g-C3N4-OH具有与实施例2基本一致的红外光谱图谱，对应位置的羟基特征峰的强度均强于g-C3N4。The infrared spectra of gC 3 N 4 prepared in Comparative Example 1 and gC 3 N 4 -OH prepared in Example 2 were measured, and the results are shown in Figure 4. Compared with gC 3 N 4 , the intensity of the hydroxyl characteristic peak of gC 3 N 4 -OH at 3325 cm -1 is higher, indicating that the solvothermal process causes hydroxyl groups to be grafted on the surface of gC 3 N 4 -OH. The gC 3 N 4 -OH prepared in Examples 1, 3, 4 and 5 have infrared spectra that are basically consistent with that of Example 2, and the intensity of the hydroxyl characteristic peaks at the corresponding positions is stronger than that of gC 3 N 4 .
测定对比例1制备的g-C3N4和实施例1制备的g-C3N4-OH的荧光发射光谱图，结果如图5所示，与g-C3N4相比，g-C3N4-OH在465nm处的荧光发射峰强度明显降低，说明g-C3N4-OH的光生电子-空穴分离效率高于g-C3N4。实施例2～5制备得到的g-C3N4-OH具有与实施例1基本一致的荧光发射光谱图。The fluorescence emission spectra of gC 3 N 4 prepared in Comparative Example 1 and gC 3 N 4 -OH prepared in Example 1 were measured, and the results are shown in Figure 5. Compared with gC 3 N 4 , the fluorescence emission peak intensity of gC 3 N 4 -OH at 465 nm is significantly reduced, indicating that the photogenerated electron-hole separation efficiency of gC 3 N 4 -OH is higher than that of gC 3 N 4. The gC 3 N 4 -OH prepared in Examples 2 to 5 has a fluorescence emission spectrum that is basically consistent with that of Example 1.
测定对比例1制备的g-C3N4和实施例3制备的g-C3N4-OH的光电流响应曲线，结果如图6所示，g-C3N4-OH的光电流密度比g-C3N4大，这说明g-C3N4-OH表面的羟基能够加快电荷传输，提高光生电子的利用效率。实施例1、2、4和5制备得到的g-C3N4-OH具有与实施例3基本一致的光电流响应曲线，光电流密度均比g-C3N4大。The photocurrent response curves of gC 3 N 4 prepared in Comparative Example 1 and gC 3 N 4 -OH prepared in Example 3 were measured, and the results are shown in Figure 6. The photocurrent density of gC 3 N 4 -OH is greater than that of gC 3 N 4 , which indicates that the hydroxyl groups on the surface of gC 3 N 4 -OH can accelerate charge transfer and improve the utilization efficiency of photogenerated electrons. The gC 3 N 4 -OH prepared in Examples 1, 2, 4 and 5 have photocurrent response curves that are basically consistent with that of Example 3, and the photocurrent densities are all greater than that of gC 3 N 4 .
测定对比例1制备的g-C3N4和实施例2制备的g-C3N4-OH的电催化析氢极化曲线图，结果如图7所示，相比于g-C3N4，g-C3N4-OH的析氢过电势变小了，这说g-C3N4表面的羟基能够降低析氢反应的势垒，促进析氢反应的进行。实施例1、3、4和5制备得到的g-C3N4-OH具有与实施例2基本一致的电催化析氢极化曲线数据，析氢过电势均小于g-C3N4。The electrocatalytic hydrogen evolution polarization curves of gC 3 N 4 prepared in Comparative Example 1 and gC 3 N 4 -OH prepared in Example 2 were measured, and the results are shown in Figure 7. Compared with gC 3 N 4 , the hydrogen evolution overpotential of gC 3 N 4 -OH is smaller, which means that the hydroxyl groups on the surface of gC 3 N 4 can reduce the potential barrier of the hydrogen evolution reaction and promote the hydrogen evolution reaction. The gC 3 N 4 -OH prepared in Examples 1, 3, 4 and 5 have electrocatalytic hydrogen evolution polarization curve data that are basically consistent with those in Example 2, and the hydrogen evolution overpotential is less than that of gC 3 N 4 .
测定对比例1制备的g-C3N4和实施例1～3制备的g-C3N4-OH的产氢总量随光照时间积累曲线图，结果如图8所示，光照3h后，g-C3N4光催化剂的总产氢量为100.3μmol/h。在同样的条件下，实施例1～3制备的g-C3N4-OH光催化剂的总产氢量分别为443.2、215.6和311.25μmol/h，其产氢量与g-C3N4相比得到明显的提升，尤其是实施例1制备得到的g-C3N4-OH光催化剂的产氢速率是g-C3N4光催化剂的4.42倍。这个结果说明表面羟基可以有效的提高g-C3N4的光催化析氢速率。实施例4和5制备的g-C3N4-OH光催化剂的总产氢量均大于g-C3N4光催化剂。The total amount of hydrogen produced by gC 3 N 4 prepared in Comparative Example 1 and gC 3 N 4 -OH prepared in Examples 1 to 3 was measured as a function of illumination time. The results are shown in FIG8 . After 3 hours of illumination, the total amount of hydrogen produced by the gC 3 N 4 photocatalyst was 100.3 μmol/h. Under the same conditions, the total amount of hydrogen produced by the gC 3 N 4 -OH photocatalysts prepared in Examples 1 to 3 was 443.2, 215.6 and 311.25 μmol/h, respectively, and the amount of hydrogen produced was significantly improved compared with that of gC 3 N 4 , especially the hydrogen production rate of the gC 3 N 4 -OH photocatalyst prepared in Example 1 was 4.42 times that of the gC 3 N 4 photocatalyst. This result shows that the surface hydroxyl group can effectively increase the photocatalytic hydrogen evolution rate of gC 3 N 4. The total amount of hydrogen produced by the gC 3 N 4 -OH photocatalysts prepared in Examples 4 and 5 was greater than that of the gC 3 N 4 photocatalyst.
综上所述，本发明通过一个简单的方法合成了富羟基化、多孔的g-C3N4-OH。与参比的g-C3N4样品比较，g-C3N4-OH表现出了更大的比表面积和更低的光生电荷复合速率。在紫外可见光照射下，负载Pt助催化剂的g-C3N4-OH的光催化分解海水析氢速率高达148.2μmol/g/h。相同条件下g-C3N4几乎没有光催化分解海水析氢的活性。In summary, the present invention synthesizes hydroxylation-rich, porous gC 3 N 4 -OH by a simple method. Compared with the reference gC 3 N 4 sample, gC 3 N 4 -OH exhibits a larger specific surface area and a lower photogenerated charge recombination rate. Under ultraviolet-visible light irradiation, the photocatalytic decomposition of seawater hydrogen evolution rate of gC 3 N 4 -OH loaded with Pt co-catalyst is as high as 148.2 μmol/g/h. Under the same conditions, gC 3 N 4 has almost no activity in photocatalytic decomposition of seawater hydrogen evolution.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.
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