CN116393155A - Carbocyclic doped g-C 3 N 4 Preparation method of heterojunction in basal plane and application of heterojunction in photo-reforming cellulose - Google Patents
Carbocyclic doped g-C 3 N 4 Preparation method of heterojunction in basal plane and application of heterojunction in photo-reforming cellulose Download PDFInfo
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Abstract
本发明属于复合材料技术领域，涉及一种碳环掺杂的g‑C3N4基面内异质结的制备方法，包括：将三聚氰胺与葡萄糖分散到去离子水中，超声充分混匀，60℃真空干燥过夜，得前驱体；将前驱体置于马弗炉中，在空气中以2.5℃/min的升温速率加热至300℃，加热1h后，温度升至400℃，继续加热1h，再以相同的升温速率加热至550℃，加热4h，自然冷却到室温后，收集，研磨成粉；用去离子水及HNO3水溶液去除杂质，离心收集，用无水乙醇、去离子水洗涤数次，烘干研磨，即得。还将所制得的催化剂，应用于光重整纤维素。本发明具有原料廉价易得，工艺简单等优点，改变了g‑C3N4分子内部结构并提高其光吸收能力，提升光生载流子的分离和迁移速率，从而提高其光催化α‑纤维素制H2活性。
The invention belongs to the technical field of composite materials, and relates to a method for preparing a carbon ring-doped g-C 3 N 4 in-plane heterojunction, comprising: dispersing melamine and glucose into deionized water, and ultrasonically mixing thoroughly, 60 ℃ vacuum drying overnight to obtain the precursor; the precursor was placed in a muffle furnace and heated to 300°C in air at a rate of 2.5°C/min. After heating for 1h, the temperature rose to 400°C and continued heating for 1h. Heat to 550°C at the same heating rate, heat for 4 hours, cool to room temperature naturally, collect, grind into powder; remove impurities with deionized water and HNO3 aqueous solution, collect by centrifugation, and wash several times with absolute ethanol and deionized water , dried and ground, that is. The prepared catalyst is also applied to light reforming cellulose. The invention has the advantages of cheap and easy-to-obtain raw materials, simple process, etc., changes the internal structure of g-C 3 N 4 molecules and improves its light absorption capacity, improves the separation and migration rate of photogenerated carriers, thereby improving its photocatalytic α -fiber Prime H2 activity.
Description
技术领域technical field
本发明属于复合材料技术领域，涉及光催化剂，尤其涉及一种碳环掺杂的g-C3N4基面内异质结的制备方法及其应用于光重整纤维素。The invention belongs to the technical field of composite materials, and relates to photocatalysts, in particular to a method for preparing a heterojunction in a carbocyclic-doped gC3N4 base plane and its application to photoreforming cellulose.
背景技术Background technique
随着全球对能源和环境的关注越来越高，如何实现清洁能源和增值化学品的生产已经成为关注的焦点。木质纤维素是最丰富的可再生碳源，具有丰富的资源和广泛的应用前景，其结构主要由三种成分组成：纤维素、半纤维素和木质素。光催化作为一种绿色、高效的技术，近年来得到了广泛地研究和应用。在此背景下，利用太阳能，通过光催化反应将木质纤维素重整产生清洁能源氢气(H2)及增值化学品已成为一种备受关注的研究领域。然而，由于木质纤维素分子结构的复杂性和分子量较大，使得产H2过程热力学上较为不利。因此，需要寻找一种低成本、绿色高效的光催化剂对木质纤维素进行光重整。As the world pays more and more attention to energy and the environment, how to achieve clean energy and the production of value-added chemicals has become the focus of attention. Lignocellulose is the most abundant renewable carbon source with abundant resources and broad application prospects. Its structure is mainly composed of three components: cellulose, hemicellulose and lignin. As a green and efficient technology, photocatalysis has been widely studied and applied in recent years. In this context, using solar energy to reform lignocellulose through photocatalytic reactions to produce clean energy hydrogen (H 2 ) and value-added chemicals has become a research field that has attracted much attention. However, due to the complex molecular structure and large molecular weight of lignocellulose, the H2 production process is thermodynamically unfavorable. Therefore, it is necessary to find a low-cost, green and efficient photocatalyst for photoreforming of lignocellulose.
近年来，提高木质纤维素光重整在可见光下的活性方面取得了重大进展，这些光催化剂大致可分为两类：第一类是金属光催化剂，如CdS、MoS2、WS2。Reisner等人利用CdS/CdOx量子点建立了高效的光重整木质纤维素体系(Wakerley,D.,Kuehnel,M.,Orchard,K.et al.,Nat.Energy,2017,2,17021)，在λ>400nm可见光照射下，产H2速率为0.556μmol h-1。为了减少金属消耗，保护环境，第二类非金属光催化剂被大量研究。例如，以NiP作为助催化剂的、氰基功能化的氮化碳(NCNCNx)(Hatice Kasap,Demetra S.Achilleos,AilunHuang,and Erwin Reisner,J.Am.Chem.Soc.2018,140,11604-11607)，在λ>400nm可见光照射下实现了48.6μmol g-1h-1的产氢速率。此外，Teng等人通过在石墨烯上掺杂S和N制备了SNGODs催化剂(Van-Can Nguyen,Dipak B.Nimbalkar,Le D.Nam,Yuh-Lang Lee,andHsisheng Teng,ACS Catalysis,2021,11,4955-4967)，提高了可见光吸收，在Pt作为助催化剂情况下，光重整木质纤维素过程中催化剂在λ＝550nm处的H2表观量子产率(AQY)达到3.4％。但上述催化剂中都含有一定的金属元素，成本较高且对环境有一定污染。In recent years, significant progress has been made in improving the activity of lignocellulose photoreforming under visible light. These photocatalysts can be roughly divided into two categories: the first category is metal photocatalysts, such as CdS, MoS 2 , and WS 2 . Reisner et al. used CdS/CdO x quantum dots to establish an efficient photoreforming lignocellulose system (Wakerley, D., Kuehnel, M., Orchard, K. et al., Nat. Energy, 2017, 2, 17021) , under the irradiation of λ>400nm visible light, the H 2 production rate is 0.556μmol h -1 . In order to reduce metal consumption and protect the environment, the second type of metal-free photocatalysts has been extensively studied. For example, cyano-functionalized carbon nitride ( NCN CN x ) with NiP as a co-catalyst (Hatice Kasap, Demetra S. Achilleos, Ailun Huang, and Erwin Reisner, J. Am. Chem. Soc. 2018, 140, 11604 -11607), and achieved a hydrogen production rate of 48.6 μmol g -1 h -1 under λ>400nm visible light irradiation. In addition, Teng et al. prepared SNGODs catalysts by doping S and N on graphene (Van-Can Nguyen, Dipak B.Nimbalkar, Le D.Nam, Yuh-Lang Lee, and Hsisheng Teng, ACS Catalysis, 2021,11, 4955-4967), improved visible light absorption, and in the case of Pt as a cocatalyst, the apparent quantum yield (AQY) of H2 at λ = 550nm of the catalyst reached 3.4% in the process of photoreforming lignocellulose. However, the above-mentioned catalysts all contain certain metal elements, which are costly and cause some pollution to the environment.
类石墨相氮化碳(g-C3N4)是一种低成本、绿色环保的非金属材料，具有良好的化学与热稳定性。g-C3N4的带隙宽度为2.7eV左右，具有良好的可见光响应。但是，体相g-C3N4自身存在着一些缺点，比如其光生电子空穴复合率较高、比表面积较小以及对可见光的利用率低等。为了提高g-C3N4太阳光利用率和光催化木质纤维素活性，构建碳环掺杂的g-C3N4基面内异质结体系是一种有效地提高其光催化活性的良好策略。Graphite-like carbon nitride (gC 3 N 4 ) is a low-cost, green and environmentally friendly non-metallic material with good chemical and thermal stability. The bandgap width of gC 3 N 4 is about 2.7eV, and it has good visible light response. However, bulk gC 3 N 4 has some disadvantages, such as high photogenerated electron-hole recombination rate, small specific surface area, and low utilization rate of visible light. In order to improve the solar light utilization efficiency and photocatalytic lignocellulose activity of gC 3 N 4 , constructing the heterojunction system of gC 3 N 4 basal plane with carbocycle doping is a good strategy to effectively improve its photocatalytic activity.
发明内容Contents of the invention
本发明的目的在于提供一种简单快捷的碳环掺杂的g-C3N4基面内异质结的制备方法，并将应其用于光催化α-纤维素制H2协同生产增值化学品。The purpose of the present invention is to provide a simple and rapid preparation method of heterojunction in the gC 3 N 4 base plane doped with carbocycles, and apply it to the photocatalytic α-cellulose to H 2 synergistic production of value-added chemicals .
技术方案Technical solutions
一种碳环掺杂的g-C3N4基面内异质结的制备方法，包括如下步骤：A method for preparing a carbocyclic doped gC 3 N 4 basal in-plane heterojunction, comprising the steps of:
A、将三聚氰胺与葡萄糖分散到去离子水中，超声使其充分混匀，50℃水浴中搅拌1h，60℃真空干燥过夜，至水分完全除去，所得前驱体干燥备用；A. Disperse melamine and glucose into deionized water, mix them thoroughly with ultrasound, stir in a water bath at 50°C for 1 hour, and dry in vacuum at 60°C overnight until the water is completely removed, and the resulting precursor is dried for use;
B、将前驱体置于马弗炉中，在空气中以2.5℃/min的升温速率加热至300℃，加热1h后，温度升至400℃，继续加热1h，再以相同的升温速率加热至550℃，加热4h，自然冷却到室温后，收集，研磨成粉；B. Put the precursor in a muffle furnace and heat it to 300°C in air at a heating rate of 2.5°C/min. After heating for 1 hour, the temperature rises to 400°C. Continue heating for 1 hour, and then heat at the same heating rate to Heat at 550°C for 4 hours, cool to room temperature naturally, collect and grind into powder;
C、粉末用去离子水将残余的水溶性物质冲洗干净，转入HNO3水溶液中超声分散1h，然后80℃水浴中搅拌2h以去除酰胺，离心收集，用无水乙醇、去离子水洗涤数次，烘干研磨，即得。C. Rinse the powder with deionized water to remove the remaining water-soluble substances, transfer it to HNO 3 aqueous solution for ultrasonic dispersion for 1 hour, then stir in a water bath at 80°C for 2 hours to remove amides, collect by centrifugation, and wash with absolute ethanol and deionized water for several times, drying and grinding, that is.
本发明较优公开例中，步骤A，参与反应的三聚氰胺、葡萄糖与去离子水的质量、体积比为10g:0.30～0.50g:50mL，优选10g:0.40g:50mL；超声时间为30min。In the preferred disclosed example of the present invention, in step A, the mass and volume ratio of melamine, glucose and deionized water participating in the reaction is 10g:0.30-0.50g:50mL, preferably 10g:0.40g:50mL; the ultrasonic time is 30min.
本发明较优公开例中，步骤C所述HNO3水溶液的浓度为0.5mol/L。In the preferred disclosed example of the present invention, the concentration of the HNO 3 aqueous solution in step C is 0.5 mol/L.
本发明所制得的碳环掺杂的g-C3N4基面内异质结，用透射电镜(TEM)观察所制催化剂之形貌，其具有和体相g-C3N4相似的层状堆叠片状结构(如图1所示)，呈现出更多的微纳米结构，更薄更透明，包含有尺寸更小的结构；图2的扫描电镜(SEM)图像也证实了这一点。The carbon ring-doped gC 3 N 4 basal in-plane heterojunction prepared by the present invention, the morphology of the prepared catalyst was observed with a transmission electron microscope (TEM), and it has a layered stack similar to the bulk phase gC 3 N 4 The sheet-like structure (as shown in Figure 1) presents more micro-nano structures, is thinner and more transparent, and contains smaller structures; this is also confirmed by the scanning electron microscope (SEM) image in Figure 2.
本发明还有一个目的在于，将所制得的催化剂，应用于光重整有机高分子，特别是纤维素。Another object of the present invention is to apply the prepared catalyst to light reforming of organic polymers, especially cellulose.
光催化实验在玻璃光反应器中进行，用橡胶隔层密封，步骤为：The photocatalytic experiment was carried out in a glass photoreactor, sealed with a rubber interlayer, and the steps were as follows:
1、将20mg催化剂和1gα-纤维素分散在50mL10mol/L的NaOH水溶液中，然后用橡胶圈和玻璃瓶盖密封反应瓶，反应前，溶液需超声10min，使催化剂和α-纤维素均匀分散；1. Disperse 20mg of catalyst and 1g of α-cellulose in 50mL of 10mol/L NaOH aqueous solution, and then seal the reaction bottle with a rubber ring and a glass bottle cap. Before the reaction, the solution needs to be ultrasonicated for 10 minutes to make the catalyst and α-cellulose evenly dispersed;
2、用惰性气体Ar气对***进行净化至少20min，以去除空气；使用配有λ≥630nm滤光片的氙灯(300W)对反应瓶进行24h光照，同时持续搅拌；2. Purify the system with inert gas Ar gas for at least 20 minutes to remove air; use a xenon lamp (300W) equipped with a λ≥630nm filter to illuminate the reaction bottle for 24 hours while continuously stirring;
以Ar气(99.999％)为载气，配备分子筛
3、通过液相色谱(配备Agilent TC-C18色谱柱)对反应后的液相产物进行分析，以0.05mol/L的KH2PO4和乙腈溶液为流动相，测试α-纤维素转化生成的增值化学品。3. Analyze the liquid phase product after the reaction by liquid chromatography (equipped with Agilent TC-C18 chromatographic column), and use 0.05mol/L of KH 2 PO 4 and acetonitrile solution as mobile phases to test the α-cellulose conversion generated Value-added chemicals.
有益效果Beneficial effect
本发明以三聚氰胺为原料，葡萄糖作为碳源，通过热共轭法合成碳环掺杂的面内异质结光催化剂CN-Cx，该方法改变了g-C3N4分子内部结构并提高了其光吸收能力，有效提升光生载流子的分离和迁移速率，提高其光催化α-纤维素制H2活性。利用简单快捷的方法合成近红外可响应的g-C3N4光催化材料，并在λ≥630nm光照射下具有良好的光重整α-纤维素产H2活性。本发明具有原料廉价易得，工艺简单等优点，投入的成本低，需要的能耗少，便于大批量生产，且无毒无害，符合节能环保的要求。The present invention uses melamine as raw material and glucose as carbon source to synthesize carbon ring-doped in-plane heterojunction photocatalyst CN-C x by thermal conjugation method. This method changes the internal structure of gC 3 N 4 molecules and improves its The light absorption ability can effectively improve the separation and migration rate of photogenerated carriers, and improve its photocatalytic activity of α-cellulose to produce H 2 . A near-infrared-responsive gC 3 N 4 photocatalytic material was synthesized by a simple and rapid method, and has good photoreformation activity of α-cellulose to produce H 2 under λ≥630nm light irradiation. The invention has the advantages of cheap and easy-to-obtain raw materials, simple process, etc., low input cost, less energy consumption, convenient mass production, non-toxic and harmless, and meets the requirements of energy saving and environmental protection.
附图说明Description of drawings
图1.体相g-C3N4(a)和实施例3所制催化剂(b)的TEM图；Fig. 1. bulk phase gC 3 N 4 (a) and the TEM figure of the prepared catalyst (b) of embodiment 3;
图2.体相g-C3N4(a)和实施例3所制催化剂(b)的SEM图；Fig. 2. bulk phase gC 3 N 4 (a) and the SEM figure of the catalyst (b) that embodiment 3 makes;
图3.实施例1-5所制备样品及体相g-C3N4的XRD谱图；Fig. 3. the sample prepared in embodiment 1-5 and the XRD spectrogram of bulk phase gC 3 N 4 ;
图4.实施例3所制备样品及体相g-C3N4的固相13C-NMR；Fig. 4. The solid phase 13 C-NMR of the sample prepared in Example 3 and the bulk phase gC 3 N 4 ;
图5.实施例1-5所制备样品及体相g-C3N4的紫外可见漫反射吸收光谱(UV-Vis)；Fig. 5. the ultraviolet-visible diffuse reflectance absorption spectrum (UV-Vis) of sample prepared in embodiment 1-5 and bulk phase gC 3 N 4 ;
图6.实施例1-5所制备样品及体相g-C3N4的Tauc图；Fig. 6. Tauc figure of sample prepared in embodiment 1-5 and bulk phase gC 3 N 4 ;
图7.实施例3所制备样品及体相g-C3N4的稳态PL测试图；Fig. 7. the sample prepared in embodiment 3 and the steady-state PL test figure of bulk phase gC 3 N 4 ;
图8.实施例1-5所制备样品在λ≥630nm光照和无任何催化剂的情况下，在10mol/LNaOH溶液里24h的光重整α-纤维素产H2图；Fig. 8. the sample prepared in embodiment 1-5 under the situation of λ≥630nm illumination and without any catalyst, in 10mol/LNaOH solution 24h photoreformation α-cellulose produces H 2 figure;
图9.实施例3所制备样品经光重整后的液相产物糖类的测试结果图。Fig. 9 is a diagram of test results of sugars in the liquid phase of the sample prepared in Example 3 after photoreforming.
具体实施方式Detailed ways
下面结合实施例对本发明进行详细说明，以使本领域技术人员更好地理解本发明，但本发明并不局限于以下实施例。The present invention will be described in detail below in conjunction with the examples, so that those skilled in the art can better understand the present invention, but the present invention is not limited to the following examples.
体相g-C3N4的制备为现有技术，合成步骤为：称取10g三聚氰胺置于玛瑙研钵中，充分研磨均匀5min得到粉末；放入坩埚内，置于马弗炉以2.5℃/min的升温速度升温至550℃，煅烧4h，自然冷却至室温，即得体相g-C3N4。The preparation of the bulk phase gC 3 N 4 is an existing technology, and the synthesis steps are as follows: weigh 10 g of melamine and place it in an agate mortar, grind it thoroughly for 5 minutes to obtain a powder; The heating rate is increased to 550°C, calcined for 4 hours, and naturally cooled to room temperature to obtain the bulk phase gC 3 N 4 .
实施例1Example 1
一种碳环掺杂的g-C3N4基面内异质结的制备方法，包括如下步骤：A method for preparing a carbocyclic doped gC 3 N 4 basal in-plane heterojunction, comprising the steps of:
1、将10g三聚氰胺与0.30g葡萄糖进行混合，完全分散到50mL去离子水中，超声30min使其充分混匀，在50℃水浴下稳定搅拌，然后在60℃真空干燥烘箱中干燥一夜，直至水分完全除去，所得前驱体干燥备用；1. Mix 10g of melamine with 0.30g of glucose, completely disperse it in 50mL of deionized water, ultrasonically mix it well for 30 minutes, stir it stably in a water bath at 50°C, and then dry it in a vacuum drying oven at 60°C overnight until the water is completely removed, the resulting precursor is dried for subsequent use;
2、将上述所得的前驱体，置于在马弗炉中以2.5℃/min的升温速度加热至300℃，加热1h后，使温度升至400℃，加热1h，然后再以相同的升温速度加热至550℃，加热4h。在自然冷却到室温后，收集和研磨以便进一步处理；2. Put the precursor obtained above in a muffle furnace and heat it up to 300°C at a heating rate of 2.5°C/min. After heating for 1 hour, raise the temperature to 400°C, heat it for 1 hour, and then use the same heating rate Heated to 550°C for 4h. After natural cooling to room temperature, collected and ground for further processing;
3、热处理后的样品用去离子水冲洗3次，去除残余的水溶性物质。然后在0.5mol/LHNO3水溶液中超声分散1h，并在80℃下稳定搅拌2h以去除酰胺。最终产物离心收集，用无水乙醇洗涤，然后用去离子水洗涤数次，3. The heat-treated samples were rinsed three times with deionized water to remove residual water-soluble substances. It was then ultrasonically dispersed in 0.5 mol/L HNO3 aqueous solution for 1 h, and stirred steadily at 80 °C for 2 h to remove the amide. The final product was collected by centrifugation, washed with absolute ethanol, and then washed several times with deionized water,
烘干研磨后得到样品B(记为CN-C0.30)。Sample B (denoted as CN-C 0.30 ) was obtained after drying and grinding.
用所制备的光催化剂进行光重整α-纤维素，反应24h后，测得生成的H2量为22.16μmol。The prepared photocatalyst was used to photoreform α-cellulose. After 24 hours of reaction, the amount of H 2 generated was measured to be 22.16 μmol.
实施例2Example 2
一种碳环掺杂的g-C3N4基面内异质结的制备方法，包括如下步骤：A method for preparing a carbocyclic doped gC 3 N 4 basal in-plane heterojunction, comprising the steps of:
1、将10g三聚氰胺与0.35g葡萄糖进行混合，完全分散到50mL去离子水中，超声30min使其充分混匀，在50℃水浴下稳定搅拌，然后在60℃1. Mix 10g of melamine and 0.35g of glucose, completely disperse it in 50mL of deionized water, ultrasonically mix it well for 30min, stir it stably in a water bath at 50°C, and then put it in a water bath at 60°C
真空干燥烘箱中干燥一夜，直至水分完全除去，所得前驱体干燥备用；Dry in a vacuum drying oven overnight until the water is completely removed, and the obtained precursor is dried for later use;
2、将上述所得的前驱体，置于在马弗炉中以2.5℃/min的升温速度加热至300℃，加热1h后，使温度升至400℃，加热1h，然后再以相同的升温速度加热至550℃，加热4h。在自然冷却到室温后，收集和研磨以便进一步处理；2. Place the precursor obtained above in a muffle furnace and heat it up to 300°C at a heating rate of 2.5°C/min. After heating for 1 hour, raise the temperature to 400°C, heat it for 1 hour, and then use the same heating rate Heated to 550°C for 4h. After natural cooling to room temperature, collected and ground for further processing;
3、热处理后的样品用去离子水冲洗3次，去除残余的水溶性物质。然后在0.5mol/LHNO3水溶液中超声分散1h，并在80℃下稳定搅拌2h以去除酰胺。最终产物离心收集，用无水乙醇洗涤，然后用去离子水洗涤数次，3. The heat-treated samples were rinsed three times with deionized water to remove residual water-soluble substances. It was then ultrasonically dispersed in 0.5 mol/L HNO3 aqueous solution for 1 h, and stirred steadily at 80 °C for 2 h to remove the amide. The final product was collected by centrifugation, washed with absolute ethanol, and then washed several times with deionized water,
烘干研磨后得到样品B(记为CN-C0.35)。Sample B (denoted as CN-C 0.35 ) was obtained after drying and grinding.
用所制备的光催化剂进行光重整α-纤维素，反应24h后，测得生成的H2量为26.91μmol。The prepared photocatalyst was used to photoreform α-cellulose. After 24 hours of reaction, the amount of H 2 generated was measured to be 26.91 μmol.
实施例3Example 3
一种碳环掺杂的g-C3N4基面内异质结的制备方法，包括如下步骤：A method for preparing a carbocyclic doped gC 3 N 4 basal in-plane heterojunction, comprising the steps of:
1、将10g三聚氰胺与0.40g葡萄糖进行混合，完全分散到50mL去离子水中，超声30min使其充分混匀，在50℃水浴下稳定搅拌，然后在60℃真空干燥烘箱中干燥一夜，直至水分完全除去，所得前驱体干燥备用；1. Mix 10g of melamine with 0.40g of glucose, completely disperse it in 50mL of deionized water, ultrasonically mix it for 30 minutes, stir it stably in a water bath at 50°C, and then dry it in a vacuum drying oven at 60°C overnight until the water is completely removed, the resulting precursor is dried for subsequent use;
2、将上述所得的前驱体，置于在马弗炉中以2.5℃/min的升温速度加热至300℃，加热1h后，使温度升至400℃，加热1h，然后再以相同的升温速度加热至550℃，加热4h。在自然冷却到室温后，收集和研磨以便进一步处理；2. Place the precursor obtained above in a muffle furnace and heat it up to 300°C at a heating rate of 2.5°C/min. After heating for 1 hour, raise the temperature to 400°C, heat it for 1 hour, and then use the same heating rate Heated to 550°C for 4h. After natural cooling to room temperature, collected and ground for further processing;
3、热处理后的样品用去离子水冲洗3次，去除残余的水溶性物质。然后在0.5mol/LHNO3水溶液中超声分散1h，并在80℃下稳定搅拌2h以去除酰胺。最终产物离心收集，用无水乙醇洗涤，然后用去离子水洗涤数次，3. The heat-treated samples were rinsed three times with deionized water to remove residual water-soluble substances. It was then ultrasonically dispersed in 0.5 mol/L HNO3 aqueous solution for 1 h, and stirred steadily at 80 °C for 2 h to remove the amide. The final product was collected by centrifugation, washed with absolute ethanol, and then washed several times with deionized water,
烘干研磨后得到样品B(记为CN-C0.40)。Sample B (denoted as CN-C 0.40 ) was obtained after drying and grinding.
用所制备的光催化剂进行光重整α-纤维素，反应24h后，测得生成的H2量为48.80μmol。The prepared photocatalyst was used to photoreform α-cellulose. After 24 hours of reaction, the amount of H 2 generated was measured to be 48.80 μmol.
实施例4Example 4
一种碳环掺杂的g-C3N4基面内异质结的制备方法，包括如下步骤：A method for preparing a carbocyclic doped gC 3 N 4 basal in-plane heterojunction, comprising the steps of:
1、将10g三聚氰胺与0.45g葡萄糖进行混合，完全分散到50mL去离子水中，超声30min使其充分混匀，在50℃水浴下稳定搅拌，然后在60℃1. Mix 10g of melamine with 0.45g of glucose, completely disperse it in 50mL of deionized water, ultrasonically mix it well for 30min, stir it stably in a water bath at 50°C, and then put it in a water bath at 60°C
真空干燥烘箱中干燥一夜，直至水分完全除去，所得前驱体干燥备用；Dry in a vacuum drying oven overnight until the water is completely removed, and the obtained precursor is dried for later use;
2、将上述所得的前驱体，置于在马弗炉中以2.5℃/min的升温速度加热至300℃，加热1h后，使温度升至400℃，加热1h，然后再以相同的升温速度加热至550℃，加热4h。在自然冷却到室温后，收集和研磨以便进一步处理；2. Put the precursor obtained above in a muffle furnace and heat it up to 300°C at a heating rate of 2.5°C/min. After heating for 1 hour, raise the temperature to 400°C, heat it for 1 hour, and then use the same heating rate Heated to 550°C for 4h. After natural cooling to room temperature, collected and ground for further processing;
3、热处理后的样品用去离子水冲洗3次，去除残余的水溶性物质。然后在0.5mol/LHNO3水溶液中超声分散1h，并在80℃下稳定搅拌2h以去除酰胺。最终产物离心收集，用无水乙醇洗涤，然后用去离子水洗涤数次，3. The heat-treated samples were rinsed three times with deionized water to remove residual water-soluble substances. It was then ultrasonically dispersed in 0.5 mol/L HNO3 aqueous solution for 1 h, and stirred steadily at 80 °C for 2 h to remove the amide. The final product was collected by centrifugation, washed with absolute ethanol, and then washed several times with deionized water,
烘干研磨后得到样品B(记为CN-C0.45)。Sample B (denoted as CN-C 0.45 ) was obtained after drying and grinding.
用所制备的光催化剂进行光重整α-纤维素，反应24h后，测得生成的H2量为19.34μmol。The prepared photocatalyst was used to photoreform α-cellulose. After 24 hours of reaction, the amount of H 2 generated was measured to be 19.34 μmol.
实施例5Example 5
一种碳环掺杂的g-C3N4基面内异质结的制备方法，包括如下步骤：A method for preparing a carbocyclic doped gC 3 N 4 basal in-plane heterojunction, comprising the steps of:
1、将10g三聚氰胺与0.50g葡萄糖进行混合，完全分散到50mL去离子水中，超声30min使其充分混匀，在50℃水浴下稳定搅拌，然后在60℃1. Mix 10g of melamine and 0.50g of glucose, completely disperse it in 50mL of deionized water, ultrasonically mix it well for 30 minutes, stir it stably in a water bath at 50°C, and then heat it at 60°C
真空干燥烘箱中干燥一夜，直至水分完全除去，所得前驱体干燥备用；Dry in a vacuum drying oven overnight until the water is completely removed, and the obtained precursor is dried for later use;
2、将上述所得的前驱体，置于在马弗炉中以2.5℃/min的升温速度加热至300℃，加热1h后，使温度升至400℃，加热1h，然后再以相同的升温速度加热至550℃，加热4h。在自然冷却到室温后，收集和研磨以便进一步处理；2. Place the precursor obtained above in a muffle furnace and heat it up to 300°C at a heating rate of 2.5°C/min. After heating for 1 hour, raise the temperature to 400°C, heat it for 1 hour, and then use the same heating rate Heated to 550°C for 4h. After natural cooling to room temperature, collected and ground for further processing;
3、热处理后的样品用去离子水冲洗3次，去除残余的水溶性物质。然后在0.5mol/LHNO3水溶液中超声分散1h，并在80℃下稳定搅拌2h以去除酰胺。最终产物离心收集，用无水乙醇洗涤，然后用去离子水洗涤数次，3. The heat-treated samples were rinsed three times with deionized water to remove residual water-soluble substances. It was then ultrasonically dispersed in 0.5 mol/L HNO3 aqueous solution for 1 h, and stirred steadily at 80 °C for 2 h to remove the amide. The final product was collected by centrifugation, washed with absolute ethanol, and then washed several times with deionized water,
烘干研磨后得到样品B(记为CN-C0.50)。Sample B (denoted as CN-C 0.50 ) was obtained after drying and grinding.
用所制备的光催化剂进行光重整α-纤维素，反应24h后，测得生成的H2量为11.31μmol。The prepared photocatalyst was used to photoreform α-cellulose. After 24 hours of reaction, the amount of H 2 generated was measured to be 11.31 μmol.
本发明在三聚氰胺中控制加入不同量的葡萄糖，采用热共轭法合成了碳环掺杂的CN-Cx面内异质结光催化剂，在λ≥630nm的光照下，分别考察了在相同催化剂量(20mg)和无任何助催化剂的条件下光重整α-纤维素产H2性能，并探寻最佳修饰剂用量。光催化结果表明适当的葡萄糖处理后的g-C3N4光催化活性明显提高。0.40g葡萄糖处理的光催化剂光催化α-纤维素产H2量最多，高达48.8μmol。在此光催化反应过程中协同产生一些增值化学品，实现了清洁能源和增值化学品的协同生产。The present invention controls the addition of different amounts of glucose in melamine, and synthesizes the carbon ring-doped CN-Cx in-plane heterojunction photocatalyst by thermal conjugation method. (20mg) and without any co-catalyst under the condition of photoreforming α-cellulose to produce H 2 performance, and to explore the optimal amount of modifier. The photocatalytic results showed that the photocatalytic activity of gC 3 N 4 was significantly improved after proper glucose treatment. The photocatalyst treated with 0.40g glucose photocatalyzed α-cellulose to generate the most H 2 , up to 48.8 μmol. Some value-added chemicals are synergistically produced during this photocatalytic reaction, realizing the synergistic production of clean energy and value-added chemicals.
用透射电镜(TEM)观察了体相g-C3N4和实施例3所制催化剂的表面形貌和结构。如图1所示，实施例3所制催化剂比体相g-C3N4更薄、更光滑，具有均匀致密的光滑表面层状结构，图2的扫描电镜(SEM)图像也证实了这一点。The surface morphology and structure of the bulk gC 3 N 4 and the catalyst prepared in Example 3 were observed with a transmission electron microscope (TEM). As shown in Figure 1, the catalyst prepared in Example 3 is thinner and smoother than the bulk gC 3 N 4 , and has a uniform and compact smooth surface layered structure, which is also confirmed by the scanning electron microscope (SEM) image in Figure 2 .
本发明所制得的碳环掺杂的g-C3N4面内异质结构由X射线衍射(XRD)确定，如图3所示，图中13°，27°衍射峰归属于g-C3N4的(100)、(002)晶面峰，说明改性后的催化剂仍保留着g-C3N4的基本结构，出现的两个衍射峰归属于g-C3N4的特征峰，与标准卡片(JCPDS No.87-1526)相符合。该谱图表明通过少量葡萄糖改性后，g-C3N4基本结构并没有明显破坏，说明葡萄糖的修饰作用是切实可行的。The carbocyclic doped gC 3 N 4 in-plane heterostructure obtained by the present invention is determined by X-ray diffraction (XRD), as shown in Figure 3, the 13° and 27° diffraction peaks in the figure belong to gC 3 N 4 (100), (002) crystal plane peaks, indicating that the modified catalyst still retains the basic structure of gC 3 N 4 , and the two diffraction peaks that appear belong to the characteristic peaks of gC 3 N 4 , which are consistent with the standard card (JCPDS No.87-1526) is consistent. The spectrogram shows that the basic structure of gC 3 N 4 is not obviously destroyed after being modified by a small amount of glucose, indicating that the modification of glucose is feasible.
图4为实施例3所制备样品的固相13C-NMR，分别在156.4ppm和164.7ppm出现了两个十分强烈的g-C3N4本体特征峰，分别归属于C1原子(C-N3)和C2原子[CN2-(NHx)]的化学位移。此外，出现一个新的弱峰，说明碳环成功引入g-C3N4结构中。Figure 4 is the solid-phase 13 C-NMR of the sample prepared in Example 3. Two very strong gC 3 N 4 bulk characteristic peaks appeared at 156.4ppm and 164.7ppm respectively, which belonged to C1 atom (CN 3 ) and C2 respectively. Chemical shifts of atoms [ CN2- ( NHx )]. In addition, a new weak peak appeared, indicating that the carbocycle was successfully introduced into the gC3N4 structure.
如图5所示，紫外可见漫反射吸收光谱(UV-Vis)，证明随着葡萄糖掺入量的增加，三聚氰胺和葡萄糖共聚所得的g-C3N4光吸收能力增强，光吸收范围明显拓宽至近红外区，有着明显的红移现象。As shown in Figure 5, the ultraviolet-visible diffuse reflectance absorption spectrum (UV-Vis) proves that with the increase of glucose incorporation, the light absorption ability of gC 3 N 4 obtained by copolymerization of melamine and glucose is enhanced, and the light absorption range is obviously broadened to the near infrared region, with an obvious redshift phenomenon.
图6的Tauc图，表明改性后的催化剂带隙宽度相对于纯的g-C3N4明显变小，说明改性后的催化剂带隙宽度缩小。The Tauc diagram in Figure 6 shows that the bandgap width of the modified catalyst is significantly smaller than that of pure gC 3 N 4 , indicating that the bandgap width of the modified catalyst is narrowed.
如图7所示，稳态PL测试中碳环掺杂的g-C3N4面内异质结的荧光强度明显变弱，表明改性后的催化剂光生载流子复合率减小，迁移率大大提升，因此光重整α-纤维素产H2活性显著提高。从图中可以看出0.40g葡萄糖修饰的g-C3N4荧光强度变弱，表明光生载流子得到有效的分离，进而提高光重整α-纤维素产H2活性。As shown in Figure 7, the fluorescence intensity of the carbon ring-doped gC3N4 in-plane heterojunction in the steady-state PL test is significantly weaker, indicating that the recombination rate of photogenerated carriers of the modified catalyst is reduced and the mobility is greatly improved. Therefore, the H 2 production activity of photoreformed α-cellulose was significantly improved. It can be seen from the figure that the fluorescence intensity of 0.40g glucose-modified gC 3 N 4 becomes weaker, indicating that the photogenerated carriers are effectively separated, thereby improving the activity of photoreforming α-cellulose to produce H 2 .
从图8可以看出，随着葡萄糖掺入量的增加，改性催化剂产H2量呈现火山型趋势，其中0.40g葡萄糖修饰的g-C3N4产H2量最多，高达48.80μmol。这一结果说明葡萄糖过多的掺入可能抑制载流子的分离。It can be seen from Figure 8 that with the increase of the amount of glucose incorporated, the H 2 production of the modified catalyst showed a volcanic trend, and the 0.40 g glucose-modified gC 3 N 4 produced the most H 2 , up to 48.80 μmol. This result suggests that excessive incorporation of glucose may inhibit the separation of carriers.
从图9可知，光重整后的反应溶液中检测到甘露糖、葡萄糖醛酸、纤维二糖、半乳糖醛酸、半乳糖和***糖等增值化学品。It can be seen from Figure 9 that value-added chemicals such as mannose, glucuronic acid, cellobiose, galacturonic acid, galactose, and arabinose were detected in the reaction solution after photoreforming.
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。The above is only an embodiment of the present invention, and does not limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made by the description of the present invention, or directly or indirectly used in other related technical fields, shall be the same as The theory is included in the patent protection scope of the present invention.
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