Solution-based processing of carbon nitride composite for boosted photocatalytic activities

Thanks to the dissolution of bulk carbon nitride (CN), a heterojunction of CN and sulfur-doped CN was constructed via a solution-based processing way, which led to a more homogeneous composite and an improved photocatalytic H₂ production activity up to 230% with respect to that by conventional impregnating.     

Promoting condensation kinetics of polymeric carbon nitride for enhanced photocatalytic activities

Polymeric carbon nitride(CN)semiconductor by thermal condensation of N-rich precursors has attracted much attention for its capability ranging from photocatalytic and photoelectrochemical energy conversion to biosensing.However,the influence of condensation process on the final structure of CN was rarely studied,making the condensation kinetic far from be fully optimized.Herein,we report the preparation of CN by a simple condensation kinetics modulation using a faster ramping rate during the polymerization process.The modified condensation recipe was even simpler than the conventional one,but led to an improved photocatalytic H2 evolution up to 3 times without any additional chemicals or other complements.Detailed mechanism studies revealed the increase of crystallinity and surface area due to the rapid condensation played the key roles.This work would offer a more facile and effective way to prepare bulk CN for large-scale industrial applications of bulk CN with higher photocatalytic actives for sustainable energy,environmental and biosensing.     

Preparation of carbon nitride nanoparticles by nanoprecipitation method with high yield and enhanced photocatalytic activity

As an emerging 2D conjugated material,graphitic carbon nitride(CN) has attracted great research attention as important catalytic medium for transforming solar energy.Nanostructure modulation of CN is an effective way to improve catalytic activities and has been extensively investigated,but remains challenging due to complex processes,time consuming or low yield.Here,taking advantage of recent discovered good solvents for CN,a nanoprecipitation approach using poor solvents is proposed for preparation of CN nanoparticles(CN NPs).With simple processes of CN dissolution and precipitation,we can quickly synthesize CN NPs(^40 nm) with a yield of up to 50%,the highest one to the best of our knowledge.As an example of potential applications,the as-prepared CN NPs were applied to photocatalytic degradation of dyes with an evident boosted performance up to 2.5 times.This work would open a new way for batch preparation of nanostructured CN and pave its large-scale industrial applications.     

Photochemical Construction of Carbonitride Structures for Red‐Light Redox Catalysis

Metal‐free carbonitride(CN) semiconductors are appealing light‐transducers for photocatalytic redox reactions owing to the unique band gap and stability. To harness solar energy efficiently, CN catalysts that are active over a wider range of the visible spectrum are desired. Now a photochemical approach has been used to prepare a new‐type triazine‐based CN structure. The obtained CN shows extraordinary light‐harvesting characteristics, with suitable semiconductor‐redox potentials. The light absorption edge of the CN reaches up to 735 nm, which is significantly longer than that of the conventional CN semiconductor at about 460 nm. As expected, the CN can efficiently catalyze oxidation of alcohols and reduction of CO₂ with visible light, even under red‐light irradiation. The results represent an important step toward the development of red‐light‐responsive triazine‐based structures for solar applications.     

盐酸处理制备高结晶氮化碳及其增强光催化产氢活性（英文）

由于氢气燃烧具有高能量和零污染的优点,氢能一直被认为是解决环境污染和全球能源危机问题的新能源.而光催化剂可以将太阳能转化为氢能,是目前制氢最理想的方式.近年来,研究者们的目光已经转向非金属光催化剂,其中氮化碳光催化剂因其化学稳定性好、成本低和无毒性而备受关注.但是传统的利用含氮前驱体通过热聚合得到的氮化碳呈无定形或半结晶结构,导致其光催化活性很差.而熔盐法制备的结晶氮化碳(CCN)则具有优异的光催化产氢性能.但是,熔盐法得到的CCN依然没达到理想的结晶度.在本文中,我们用盐酸(HCl)洗涤处理熔盐法制备的产物,进一步提高了CCN的结晶度.结果表明,随着盐酸水溶液浓度的增加,制备样品的结晶度增大,在盐酸浓度为0.1 mol/L时,样品结晶度达到最大值.这是因为盐酸水溶液可以去除CCN末端氨基中的一些钾离子,导致聚合位点被释放,所以进一步提高了样品的结晶度.而当盐酸浓度进一步提高到0.2 mol/L时,氮化碳结构因为过高的盐酸浓度被破坏,导致结晶度反而下降.以0.1 mol/L盐酸水溶液处理得到的0.1HCCN样品具有良好的光催化产氢性能,在以三乙醇胺为牺牲剂时,其光催化产氢速率达到683.54μmol h^-1 g^-1,在420 nm处的量子效率为6.6%,光催化产氢速率分别是CCN和块状氮化碳的2倍和10倍.光催化活性的提高主要有两个原因:样品结晶度的提高和钾离子嵌入xHCCN样品的中间层.其中,样品结晶度的提高可以减少样品中的表面缺陷以及破坏结构中的氢键,从而增加了光生载流子的迁移,减少了电子空穴对的复合位点,这都非常有利于光催化反应的进行.而插入到xHCCN中间层的钾也促进了光生电子的转移.这是因为桥连的氮原子(N1)并不会被激发产生光生电子,因此抑制了光生电子在七嗪单元之间的迁移,而插入到xHCCN中间层的K可以增加电子的离域性,延长π共轭体系,从而促进光生电子的转移,进一步提高光催化产氢活性.本研究为熔盐法的进一步发展提供了新的思路.     

高活性钒酸铋的尿素沉淀法控制合成及其光催化活性增强机制研究

通过普通尿素沉淀法、超声协助和水热尿素法合成出高结晶度的单斜晶白钨矿型的钒酸铋粉末。利用XRD、SEM、DRS等手段分别对合成材料的晶型、微观形貌及光物理性质等进行研究。结果表明3种方法均能得到结晶度较高的钒酸铋颗粒,但微观形貌上有较大差异。在可见光下对难生化降解的红色染料FN-3G的降解效果表明,所合成的三种BiVO₄样品的光催化性能均较好,超声协助法和水热法合成的样品光催化活性增强的机制主要归因于结晶度的提高和比表面积的增大。结晶度的提高可降低电子和空穴复合几率,从而增强光电转换效率;而比表面积的增大主要提高了染料分子的吸附能力。     

Crystalline Carbon Nitride Semiconductors for Photocatalytic Water Splitting

Conjugated carbon nitride (CN) is an emerging and promising semiconductor photocatalyst for water photolysis owing to its unique properties. However, the traditional thermally induced polymerization of N‐containing precursors typically produces melon‐based CN solids with amorphous or semi‐crystalline structures with only moderate photocatalytic performance. Many strategies have been developed to prepare crystalline CNs (CCNs), such as high‐temperature and high‐pressure routes, ionothermal synthesis, and microwave‐assisted synthesis. In this Minireview, we summarize the progress that has been made in the synthesis of CCNs and their application in photocatalytic water splitting reactions. Three kinds of CCNs are mainly discussed according to their polymeric subunits. Challenges associated with CCNs and their future development are also included.     

Polymeric Donor–Acceptor Heterostructures for Enhanced Photocatalytic H2 Evolution without Using Pt Cocatalysts

Polymeric carbon nitride (CN) is a promising material for photocatalytic water splitting. However, CN in its pristine form tends to show moderate activity due to fast recombination of the charge carriers. The design of efficient photocatalytic system is therefore highly desired, but it still remains a great challenge in chemistry. In this work, a pyrene-based polymer able to serve as an electron donor to accelerate the interface charge carrier transfer of CN is presented. The construction of donor-acceptor (D–A) heterojunction was confirmed to significantly restrain the charge recombination and, thus, improve the proton reduction process. This study provides a promising strategy to achieve solar H₂ production in an efficient and low-cost manner.     

Synthesis of Hierarchical Macro‐/Mesoporous Solid‐Solution Photocatalysts by a Polymerization–Carbonization–Oxidation Route: The Case of Ce0.49Zr0.37Bi0.14O1.93

A hierarchical macro‐/mesoporous Ce_0.49Zr_0.37Bi_0.14O_1.93 solid‐solution network has been synthesized on a large scale by means of a simple and general polymerization–carbonization–oxidation synthetic route. The as‐prepared product has been characterized by SEM, XRD, TEM, BET surface area measurement, UV/Vis diffuse‐reflectance spectroscopy, energy‐dispersive X‐ray spectroscopy (EDS), and photoelectrochemistry measurements. The photocatalytic activity of the product has been demonstrated through the photocatalytic degradation of methyl orange. Structural characterization has indicated that the hierarchical macro‐/mesoporous solid‐solution network not only contains numerous macropores, but also possesses an interior mesoporous structure. The mesopore size and BET surface area of the network have been measured as 2–25 nm and 140.5 m² g^?1, respectively. The hierarchical macro‐/mesoporous solid‐solution network with open and accessible pores was found to be well‐preserved after calcination at 800 °C, indicating especially high thermal stability. Due to its high specific surface area, the synergistic effect of the coupling of macropores and mesopores, and its high crystallinity, the Ce_0.49Zr_0.37Bi_0.14O_1.93 solid‐solution material shows a strong structure‐induced enhancement of visible‐light harvest and exhibits significantly improved visible‐light photocatalytic activity in the photodegradation of methyl orange compared with those of its other forms, such as mesoporous hollow spheres and bulk particles.     

Improved photocatalytic activity of TiO_2 produced by an alcohothermal approach through in-situ decomposition of NH_4HCO_3

High crystallinity of TiO_2 was prepared by a modified alcohothermal method, in which titanium isopropoxide was used as the titania precursor, absolute ethanol as the reaction medium, and NH_4HCO_3 as the raw materials for release of water, ammonia and carbon dioxides via in-situ decomposition. The X-ray powder diffraction(XRD) and transmission electron microscope(TEM) measurements showed that water and ammonia from the in-situ decomposition of NH_4HCO_3 played an important role in conducting the size, shape, crystallinity and microstructure of TiO_2. The photoluminescence spectroscopy and photocurrent measurements indicated that enhanced crystallinity could hinder the recombination and promote the separation of electron-hole pairs in TiO_2, which contribute to the improvement of photocatalytic activity.Methyl orange photodegradation under UV light confirmed that high crystallinity of TiO_2 did present a high photocatalytic activity due to the effective separation of photoinduced charges.     

还原氧化石墨烯-硒化银纳米复合材料的水热合成与表征及其活性氧物种产生(英文)

A visible-light photocatalyst containing Ag2Se and reduced graphene oxide(RGO) was synthesized by a facile sonochemical-assisted hydrothermal method. X-ray diffraction, scanning electron mi-croscopy with energy-dispersive X-ray analysis, and ultraviolet-visible diffuse reflectance spectros-copy results indicated that the RGO-Ag2Se nanocomposite contained small crystalline Ag2Se nano-particles dispersed over graphene nanosheets and absorbed visible light. The high crystallinity of the nanoparticles increased photocatalytic activity by facilitating charge transport. N2 adsorp-tion-desorption measurements revealed that the RGO-Ag2Se nanocomposite contained numerous pores with an average diameter of 9 nm, which should allow reactant molecules to readily access the Ag2Se nanoparticles. The RGO-Ag2Se nanocomposite exhibited higher photocatalytic activity than bulk Ag2Se nanoparticles to degrade organic pollutant rhodamine B and industrial dye Texbrite BA-L under visible-light irradiation(λ 420 nm). The generation of reactive oxygen spe-cies in RGO-Ag2Se was evaluated through its ability to oxidize 1,5-diphenylcarbazide to 1,5-diphenylcarbazone. The small size of the Ag2Se nanoparticles in RGO-Ag2Se was related to the use of ultrasonication during their formation, revealing that this approach is attractive to form po-rous RGO-Ag2Se materials with high photocatalytic activity under visible light.     

微波辅助液相沉积法快速制备纳米氧化钛晶体

Anatase nanoparticles were successfully prepared via a facile microwave assisted liquid phase deposition （MW-LPD） process with hexafluorotitanate ammonium （NH4）2TiF6 as precursor. Compared with the conventional LPD processes, the MW-LPD technique could provide high yield quickly and crystallinity in a diluted precursor solution at a low temperature. The products were characterized by XRD and TEM. Their photocatalytic activities were also investigated by the photodegradation of methylene blue （MB） as a model molecule.     

A Borocarbonitride Ceramic Aerogel for Photoredox Catalysis

Borocarbonitride (BCN) is a new type of photocatalyst, but bulk BCN shows a large band gap, and low surface area, and moderate activity for photocatalysis. Here, a three‐dimensional (3D) porous ceramic BCN aerogel was developed as an effective photocatalyst for relevant reactions. The unique structures endow the aerogel with an adjustable band gap and a high surface area, excellent stability, and improved crystallinity, which accelerates the separation and transfer of electron‐hole pairs and promotes catalytic kinetics, thus enhancing the performance of photocatalytic reactions for hydrogen generation and carbon dioxide reduction. This work supplies a low‐cost, convenient and green synthesis method for building ceramic aerogels, and it provides a simple colloid chemistry strategy combined with boron‐containing compounds to facilitate further innovative breakthroughs in the novel ceramic aerogel materials design and development in the field of catalysis.     

Heterometal alkoxides as precursors for the preparation of porous Fe- and Mn-TiO2 photocatalysts with high efficiencies

Transition-metal-doped titanium glycolates (M-TG, with M=Fe, Mn), which are the first non-stoichiometric heterometal alkoxides, have been synthesised through a solvothermal doping approach. X-ray diffraction, UV/Vis diffuse reflectance and ESR spectroscopy revealed that the dopant ion (Fe(3+) or Mn(2+)) is substituted for Ti(4+) in the TG lattice. Fe(3+) prolongs the crystallisation time of Fe-TG, whereas Mn(2+) has a smaller effect on the crystallisation time in comparison with Fe(3+). The as-synthesised M-TG materials were used directly as single-source precursors for the preparation of metal-doped titania (M-TiO(2)) through a simple thermal treatment process. The as-prepared M-TiO(2) materials maintain the rod-like morphology of the precursors and possess a mesoporous structure with high crystallinity. It has been proved that the dopant ions are incorporated into the TiO(2) lattice at the Ti(4+) positions. The photocatalytic activities of the M-TiO(2) materials obtained were evaluated by testing the degradation of phenol under UV irradiation. From the photocatalytic results, it was concluded that high crystallinity, a large surface area and appropriate transition-metal-doping are all beneficial to the enhancement of the photocatalytic performance of the doped TiO(2) material. In addition, it was noted that in comparison with Mn-TiO(2), Fe-TiO(2) shows higher photocatalytic activity due to the better inhibition effect of Fe(3+) on recombination of photogenerated electron-hole pairs. In contrast to the conventional nanosized TiO(2) photocatalyst, the micrometre-sized M-TiO(2) particles we obtained can be easily separated and recovered after the photocatalytic reactions.     

二维/二维FeNi-LDH/g-C3N4复合光催化剂用于促进CO2光还原反应

Photocatalytic reduction of carbon dioxide into chemical fuels is a promising route to generate renewable energy and curtail the greenhouse effect. Therefore, various photocatalysts have been intensively studied for this purpose. Among them, g-C₃N₄, a 2D metal-free semiconductor, has been a promising photocatalyst because of its unique properties, such as high chemical stability, suitable electronic structure, and facile preparation. However, pristine g-C₃N₄ suffers from low solar energy conversion efficiency, owing to its small specific surface area and extensive charge recombination. Therefore, designing g-C₃N₄ (CN) nanosheets with a large specific surface area is an effective strategy for enhancing the CO₂ reduction performance. Unfortunately, the performance of CN nanosheets remains moderate due to the aforementioned charge recombination. To counter this issue, loading a cocatalyst (especially a two-dimensional (2D) one) can enable effective electron migration and suppress electron-hole recombination during photo-irradiation. Herein, CN nanosheets with a large specific surface area (97 m²·g^-1) were synthesized by a two-step calcination method, using urea as the precursor. Following this, a 2D/2D FeNi-LDH/g-C₃N₄ hybrid photocatalyst was obtained by loading a FeNi layered double hydroxide (FeNi-LDH) cocatalyst onto CN nanosheets by a simple hydrothermal method. It was found that the production rate of methanol from photocatalytic CO₂ reduction over the FeNi-LDH/g-C₃N₄ composite is significantly higher than that of pristine CN. Following a series of characterization and analysis, it was demonstrated that the FeNi-LDH/g-C₃N₄ composite photocatalyst exhibited enhanced photo-absorption, which was ascribed to the excellent light absorption ability of FeNi-LDH. The CO₂ adsorption capacity of the FeNi-LDH/g-C₃N₄ hybrid photocatalyst improved, owing to the large specific surface area and alkaline nature of FeNi-LDH. More importantly, the introduction of FeNi-LDH on the CN nanosheet surface led to the formation of a 2D/2D heterojunction with a large contact area at the interface, which could promote the interfacial separation of charge carriers and effectively inhibit the recombination of the photogenerated electrons and holes. This subsequently resulted in the enhancement of the CO₂ photo-reduction activity. In addition, by altering the loading amount of FeNi-LDH for photocatalytic performance evaluation, it was found that the optimal loading amount was 4% (w, mass fraction), with a methanol production rate of 1.64 μmol·h^-1·g^-1 (approximately 6 times that of pure CN). This study provides an effective strategy to improve the photocatalytic CO₂ reduction activity of g-C₃N₄ by employing 2D layered double hydroxide as the cocatalyst. It also proposes a protocol for the successful design of 2D/2D photocatalysts for solar energy conversion.      

Photophysics and Photocatalysis of Melem: A Spectroscopic Reinvestigation

Graphitic carbon nitride (g‐CN) is one potential metal‐free photocatalyst. The photocatalytic mechanism of g‐CN is related to the heptazine ring building unit. Melem is the simplest heptazine‐based compound and g‐CN is its polymeric product. Thus, studies on the photophysical properties of melem will help to understand the photocatalytic mechanism of heptazine‐based materials. Herein, the spectroscopic features of melem were systematically explored through measuring its absorption spectrum, fluorescence spectrum, and fluorescence decay. Both fluorescence spectroscopy and fluorescence decay measurements show that the condensation of melamine to melem causes stronger photoluminescence, whereas the condensation of melem to g‐CN causes weaker photoluminescence. In addition, all observations reveal that a mixture of monomer melem and its higher condensates is more easily obtained during the preparation of melem, and that the higher condensates of melem affect the photophysical properties of melem dominantly. The photocatalytic hydrogen evolution of melem has also been measured and the monomer melem has negligible photoinduced water‐splitting activity.     

Stability and Crystallinity of Sodium Poly(Heptazine Imide) in Photocatalysis

Poly(heptazine imide) (PHI) salts, as crystalline carbon nitrides, exhibit high photocatalytic activity and are being extensively researched, but its photochemical instability has not drawn researchers’ attention yet. Herein, sodium PHI (PHI−Na) ultrathin nanosheets with increased crystallinity, synthesized by enhancing contact of melamine with NaCl functioning as a structure-induction agent and hard template, exhibits improved photocatalytic hydrogen evolution activity, but low photochemical stability, owing to Na⁺ loss in the photocatalytic process, which, interestingly, can be enhanced by the common ion effect, e.g., addition of NaCl that is also able to remarkably increase the photoactivity with the apparent quantum yield at 420 nm reaching 41.5 %. This work aims at attracting research peers’ attention to photochemical instability of PHI salts and provides a way to enhance their crystallinity.     

The Role of Polarization in Photocatalysis

Semiconductor photocatalysis as a desirable technology shows great potential in environmental remediation and renewable energy generation, but its efficiency is severely restricted by the rapid recombination of charge carriers in the bulk phase and on the surface of photocatalysts. Polarization has emerged as one of the most effective strategies for addressing the above‐mentioned issues, thus effectively promoting photocatalysis. This review summarizes the recent advances on improvements of photocatalytic activity by polarization‐promoted bulk and surface charge separation. Highlighted is the recent progress in charge separation advanced by different types of polarization, such as macroscopic polarization, piezoelectric polarization, ferroelectric polarization, and surface polarization, and the related mechanisms. Finally, the strategies and challenges for polarization enhancement to further enhance charge separation and photocatalysis are discussed.     

Doping‐Induced Amorphization,Vacancy, and Gradient Energy Band in SnS2 Nanosheet Arrays for Improved Photoelectrochemical Water Splitting

Photoelectrochemical (PEC) water splitting is a promising strategy to convert solar energy into hydrogen fuel. However, the poor bulk charge‐separation ability and slow surface oxygen evolution reaction (OER) dynamics of photoelectrodes impede the performance. We construct In‐ and Zn/In‐doped SnS₂ nanosheet arrays through a hydrothermal method. The doping induces the simultaneous formation of an amorphous layer, S vacancies, and a gradient energy band. This leads to elevated carrier concentrations, an increased number of surface‐reaction sites, accelerated surface‐OER kinetics, and an enhanced bulk‐carrier separation efficiency with a decreased recombination rate. This efficient doping strategy allows to manipulate the morphology, crystallinity, and band structure of photoelectrodes for an improved PEC performance.     

Doping‐Induced Amorphization,Vacancy, and Gradient Energy Band in SnS2 Nanosheet Arrays for Improved Photoelectrochemical Water Splitting

Photoelectrochemical (PEC) water splitting is a promising strategy to convert solar energy into hydrogen fuel. However, the poor bulk charge‐separation ability and slow surface oxygen evolution reaction (OER) dynamics of photoelectrodes impede the performance. We construct In‐ and Zn/In‐doped SnS₂ nanosheet arrays through a hydrothermal method. The doping induces the simultaneous formation of an amorphous layer, S vacancies, and a gradient energy band. This leads to elevated carrier concentrations, an increased number of surface‐reaction sites, accelerated surface‐OER kinetics, and an enhanced bulk‐carrier separation efficiency with a decreased recombination rate. This efficient doping strategy allows to manipulate the morphology, crystallinity, and band structure of photoelectrodes for an improved PEC performance.