BiZnx/Si光电阴极的制备及其CO2还原性能研究

将CO₂转化为高附加值的化学品是实现碳循环, 缓解能源危机和环境问题的有效途径之一。金属与半导体复合电极, 利用光电耦合技术为CO₂转化提供了一种新思路。本研究通过电沉积的方法在碱刻蚀处理后的Si片上制备了双金属Bi、Zn共修饰的Si基光电阴极(BiZn_x/Si), 用于CO₂的光电催化还原。研究表明, 引入金属Bi和Zn能够改善光的吸收性能, 降低电化学阻抗, 提高电化学活性比表面积(ECSA)。其中, BiZn₂/Si最优的光电极电化学比表面积可达0.15 mF·cm^-2。除此之外, 研究发现双金属共同作用有助于增强电极对中间体*OCHO的吸附作用, 在-0.8 V(vs. RHE)电势下, 最优的光电阴极BiZn₂/Si生成HCOOH的法拉第效率高达96.1%。更重要的是, 光电阴极BiZn₂/Si的光电流强度在10 h内维持-13 mA·cm^-2, 表现出良好的性能稳定性。     

单原子催化剂在电催化还原CO2中的应用进展

化石燃料燃烧产生的温室气体CO2引发的环境问题一直是人们关注的热点.为缓解温室气体带来的环境危机和不可再生能源的枯竭,急需研究出高效处理CO2新技术.电催化还原CO2是将CO2资源化无害化的一条有效途径,该技术可行性关键取决于开发高活性和选择性的催化剂,单原子催化剂因其具有高活性、高选择性、高稳定性、可以重复循环使用等...     

铜离子价态对铜基催化剂光/电催化CO2还原性能影响的研究进展

在双碳目标下,实现CO₂光/电催化还原是缓解温室效应和提高碳资源利用率的一种前瞻性策略。然而,由于涉及多质子耦合的电子转移、碳碳偶联和氢化等过程,提高CO₂还原反应的转化产率和对单一产物的选择性仍然面临着重大的挑战。由于Cu与CO具有良好的结合能,因此铜基催化剂在提升CO₂的还原效率方面极具应用前景。本文以纳米级铜基催化剂为切入点,讨论不同价态的铜离子作光/电催化剂时,催化剂形貌、元素掺杂、与其他材料复合对CO₂还原过程的影响,着重论述目前研究中不同形貌、掺杂元素和复合催化剂在反应过程中对含Cu²⁺,Cu⁺,Cu⁰三种铜离子的催化作用,以及对还原产物的选择性和相应的法拉第效率的影响,最后对铜基催化剂未来的研究重点提出一些建议,包括Cu离子价态对生成多碳产物的机理分析、高效且有单一选择性的催化剂制备、采用先进技术进行产物种类调控。     

CdZnSe/ZnSe/ZnSeS量子点材料的制备及其量子点电致发光器件性能研究

量子点（QDs）材料由于其出色单色性,发光可调等优点,在电致器件方面得到了快速的发展。文章研究通过物理方法在QDs核生长的过程中用溶剂稀释单体的浓度,减少QDs核的生长时间,从而可在不改变化学成分比例的基础上改变QDs的发光波长。进一步通过包覆ZnSe与ZnSeS壳层对发光波长进行调制,最终得到光致波长在540 nm的绿色QDs。通过对比实验以及LaMer模型解释了发生变色的原理。仅在核的生长阶段进行干涉才能控制QDs的发光峰位。同时发现提高QDs外壳的包覆温度对QDs的缺陷的减少有积极作用。随后将得到的QDs用于制备量子点电致发光器件,在8 V电压下得到了348993 Cd/m²的亮度,以及32 Cd/A的电流效率。另外,该方法可以为其它类型的由热注入法制备的纳米材料制备提供新的思路。

     

碳量子点的制备与性能及其应用研究进展

碳量子点(CQDs)是一种零维荧光碳纳米材料,其尺寸一般低于10nm。由于其独特的荧光性质、光学稳定性、发射光谱可调性、低毒性和良好的生物相容性等优势,从而在化学与生物传感、光催化和防伪等领域起到了重要作用。综述了CQDs材料的合成方法、结构性质和在生物成像、化学传感、光催化和防伪领域的研究进展,并且对CQDs材料的发展进行了展望。     

Co2+掺杂水溶性ZnS量子点的制备及其光致发光性能

采用共沉淀法,以3-巯基丙酸为表面修饰剂,成功制备出Co2+掺杂水溶性ZnS量子点。采用X射线衍射仪、透射电子显微镜、原子发射光谱仪、紫外-可见吸收光谱仪和荧光分光光度计等,研究了Co2+掺杂剂及掺杂量对ZnS量子点的晶体结构、形貌和发光性能等的影响。结果表明:所得产物均为ZnS立方型闪锌矿结构,量子点呈不规则球形,粒径主要集中在5.2 nm左右;掺杂样品发红色荧光,发光性能明显增强,属于Co2+形成的杂质能级(4A1—4T1)与缺陷的复合发光。同时,利用红外吸收光谱对Co2+掺杂水溶性ZnS量子点的形成机理进行了初步探讨。     

量子点/环氧树脂复合材料的制备及性能

通过自组装技术将十二胺包覆到CdSe量子点表面实现量子点的氨基改性,并以三乙烯四胺为固化剂制备得到CdSe量子点/环氧树脂复合材料,研究了量子点表面氨基改性对复合材料性能的影响。通过高分辨透射电镜表征量子点的分散情况及粒径大小,X射线能谱表征量子点改性前后元素的变化,动态光散射表征量子点团簇在环氧基体中的粒度分布,紫外-可见光谱表征复合材料的透明性,荧光光谱表征复合材料的荧光性能,冲击试验表征量子点改性前后对复合材料的增韧作用。结果表明,氨基改性量子点/环氧树脂复合材料的透明度为原始量子点/环氧树脂复合材料的2倍,荧光强度为原始量子点/环氧树脂复合材料的4倍。当量子点含量为0.5%时,氨基改性量子点/环氧树脂复合材料的冲击强度达7.28 k J/m~2。     

PbS量子点/ZnO纳米片复合膜的制备及其光电化学性能

通过两步法合成PbS量子点(QDs)修饰ZnO纳米片复合膜. 首先利用电化学法在掺氟的SnO₂导电玻璃(FTO)上生长ZnO纳米片, 然后在ZnO纳米片上通过逐次化学浴法沉积PbS量子点形成PbS/ZnO复合膜. 利用扫描电子显微镜(SEM)、X射线衍射仪(XRD)详细表征了样品的表面形貌和晶体结构, 并研究了PbS/ZnO复合膜作为量子点敏化太阳能电池光阳极的紫外-可见吸收谱、光电化学性能和表面光电压谱. 对比ZnO纳米片经PbS量子点修饰前后, 发现PbS量子点修饰后光阳极的光吸收和光伏响应均从紫外区拓宽到了可见光区, 同时光电化学性能有了显著提高, 短路电流密度从敏化前的0.1 mA/cm²增加到0.7 mA/cm², 效率由0.04%增加到0.57%. 与单一ZnO纳米片相比, PbS/ZnO复合膜的表面光伏响应强度明显增强, 说明PbS与ZnO之间形成了有利于光生电荷分离的异质结, 从而导致了PbS/ZnO复合膜光电性能的增加.     

锡硫化合物包覆的水溶性硒化镉量子点的制备与表征

以Na2S、Na2SnO3、稀盐酸及水合肼为原料成功合成了锡硫化合物(Metalchal cogenidometalates,MCCs)。该化合物在离子溶液中解离出SnS44-或Sn2S46-,这两种低聚阴离子因其电子空间结构特殊而具有配位作用,故能置换CdSe量子点表面原有的长链有机配体,从而实现量子点从有机相到无机相的转移。配体交换后的量子点可以较好地分散在水、氨水、水合肼和二甲亚砜等一系列极性溶剂中。我们分别用透射电子显微镜(TEM)、紫外吸收光谱(UV)、荧光发射光谱(PL)和红外吸收光谱(FTIR)表征了CdSe的分散性、光学性质及表面配体情况。     

水相合成CdTe量子点及其性能表征

以NaTeO3为碲源,巯基乙酸(TGA)为稳定剂,合成CdTe量子点。研究Cd2+的浓度、Cd2+-TGA前驱体室温静置时间对CdTe量子点荧光光谱、荧光量子效率的影响,并用X射线粉末衍射仪和透射电子显微镜对其结晶性能、结构以及形貌进行表征。实验表明,所制备的CdTe量子点具有闪锌矿结构和球形形貌。且在Cd2+-TGA前驱体室温静置50min后参与回流,Cd2+浓度为0.00067mol/L时,荧光量子效率最高可达48.4%。     

Controllable CO2 Reduction or Hydrocarbon Oxidation Driven by Entire Solar via Silver Quantum Dots Direct Photocatalysis

The current solar-chemical-industry based on semiconductor photocatalyst is impractical. Metal catalysts are extensively employed in thermal- and electro-catalysis industries, but unsuitable for direct-driven photocatalysis. Herein, silver quantum dots (Ag-QDs) are synthesized on support via an in situ photoreduction method, and in situ photocatalysis temperature programmed dynamics chemisorption desorption analyses are designed to demonstrate that Ag-QDs should be the actual photocatalytic sites. The surface plasmon resonance of Ag-QDs could harvests entire visible solar, and the plasmon-driven charge-transfer exhibits opposite directions at the interface when supports are different. Consequently, Ag-QDs could be alternatively regulated as oxidation or reduction active centers. Furthermore, Ag-QDs excite electron tunneling transfer with adsorbate, which does not generate high-energy free-radical intermediates. As a result, the efficiencies of hydrocarbon photooxidation and CO₂ photoreduction are improved in several orders of magnitude. Evidently, the Ag-QDs direct photocatalytic technology greatly promotes solar-chemical-industry applications.     

Enhanced Photocatalytic H2‐Production Activity of CdS Quantum Dots Using Sn2+ as Cocatalyst under Visible Light Irradiation

Herein, oil‐soluble CdS quantum dots (QDs) are first prepared through a solvent‐thermal process. Then, oil‐soluble CdS QDs are changed into water‐soluble QDs via ligand exchange using mercaptopropionic acid as capping agent at pH 13. The photocatalytic performance is investigated under the visible light irradiation using glycerol as sacrificial agent and Sn²⁺ as cocatalyst. No H₂‐production activity is observed for oil‐soluble CdS QDs. Water‐soluble CdS QDs exhibit significantly enhanced hydrogen evolution rate. When the concentration of cocatalyst Sn²⁺ increases to 0.2 × 10^?3 m , the rate of hydrogen evolution reaches 1.61 mmol g^?1 h^?1, which is 24 times higher than that of the pristine water‐soluble CdS QDs. The enhanced H₂‐production efficiency is attributed to the adsorption of Sn²⁺ ions on the surface of CdS QDs that are further reduced to Sn atoms by photogenerated electrons. The in situ generated Sn atoms serve as photocatalytic cocatalyst for efficient hydrogen generation.     

Synergistically Coupling Black Phosphorus Quantum Dots with MnO2 Nanosheets for Efficient Electrochemical Nitrogen Reduction Under Ambient Conditions

The electrochemical nitrogen reduction reaction (NRR) is a promising strategy of nitrogen fixation into ammonia under ambient conditions. However, the development of electrochemical NRR is highly bottlenecked by the expensive noble metal catalysts. As a representative 2D nonmetallic material, black phosphorus (BP) has the valence electron structure similar to nitrogen, which can effectively adsorb the inactive nitrogen molecule and activate its triple bond. In addition, the relatively weak hydrogen adsorption can restrict the competitive and vigorous hydrogen evolution reaction. Herein, ultrafine BP quantum dots (QDs) are prepared via liquid‐phase exfoliation and then assembled on catalytically active MnO₂ nanosheets through van der Waals interactions. The obtained BP QDs/MnO₂ catalyst demonstrates admirable synergetic effects in electrochemical NRR. The monodisperse BP QDs providing major activity manifest excellent ammonia production steadily with high selectivity, which benefits from the robust confinement of the BP QDs on the wrinkled MnO₂ nanosheets with decent activity. A high ammonia yield rate of 25.3 µg h^?1 mg_cat.^?1 and faradic efficiency of 6.7% can be achieved at ?0.5 V (vs RHE) in 0.1 m Na₂SO₄ electrolyte, which are dramatically superior to either component. The isotopic labelling and other control tests further exclude the external contamination possibility and attest the genuine activity.     

Smart Utilization of Carbon Dots in Semiconductor Photocatalysis

Efficient capture of solar energy will be critical to meeting the energy needs of the future. Semiconductor photocatalysis is expected to make an important contribution in this regard, delivering both energy carriers (especially H₂) and valuable chemical feedstocks under direct sunlight. Over the past few years, carbon dots (CDs) have emerged as a promising new class of metal‐free photocatalyst, displaying semiconductor‐like photoelectric properties and showing excellent performance in a wide variety of photoelectrochemical and photocatalytic applications owing to their ease of synthesis, unique structure, adjustable composition, ease of surface functionalization, outstanding electron‐transfer efficiency and tunable light‐harvesting range (from deep UV to the near‐infrared). Here, recent advances in the rational design of CDs‐based photocatalysts are highlighted and their applications in photocatalytic environmental remediation, water splitting into hydrogen, CO₂ reduction, and organic synthesis are discussed.     

调控CuO表面性质选择性电催化还原CO2制HCOOH

电催化二氧化碳还原反应可将温室气体二氧化碳转化为化工原料或者有机燃料,为克服全球变暖和电能向化学能转化提供了一条可行途径.该技术的主要挑战是产物分布广,导致单一产物选择性低,而调控催化剂的表面性质是解决这一难题的可行策略.本研究通过对氧化亚铜、硫化亚铜进行氧化制备表面性质不同的氧化铜,其中,氧化硫化亚铜制得的CuO-F...     

Multilayer-Cavity Tandem Catalyst for Profiling Sequentially Coupling of Intermediate CO in Electrocatalytic Reduction Reaction of CO2 to Multi-Carbon Products

Electrochemical CO₂ reduction reaction (CO₂RR) is an effective approach to address CO₂ emission, promote recycling, and synthesize high-value multi-carbon (C₂₊) chemicals for storing renewable electricity in the long-term. The construction of multilayer-bound nanoreactors to achieve management of intermediate CO is a promising strategy for tandem to C₂₊ products. In this study, a series of Ag@Cu₂O nanoreactors consisting of an Ag-yolk and a multilayer confined Cu shell is designed to profile electrocatalytic CO₂RR reactions. The optimized Ag@Cu₂O-2 nanoreactor exhibits a 74% Faradaic efficiency during the C₂₊ pathway and remains stable for over 10 h at a bias current density of 100 mA cm⁻². Using the finite element method, this model determines that the certain volume of cavity in the Ag@Cu₂O nanoreactors facilitates on-site CO retention and that multilayers of Cu species favor CO capture. Density functional theory calculations illustrate that the biased generation of ethanol products may arise from the (100)/(111) interface of the Cu layer. In-depth explorations in multilayer-bound nanoreactors provide structural and interfacial guidance for sequential coupling of CO₂RR intermediates for efficient C₂₊ generation.     

Electrode Materials Engineering in Electrocatalytic CO2 Reduction: Energy Input and Conversion Efficiency

Electrocatalytic CO₂ reduction (ECR) is a promising technology to simultaneously alleviate CO₂-caused climate hazards and ever-increasing energy demands, as it can utilize CO₂ in the atmosphere to provide the required feedstocks for industrial production and daily life. In recent years, substantial progress in ECR systems has been achieved by the exploitation of various novel electrode materials. The anodic materials and cathodic catalysts that have, respectively, led to high-efficiency energy input and effective heterogenous catalytic conversion in ECR systems are comprehensively reviewed. Based on the differences in the nature of energy sources and the role of materials used at the anode, the fundamentals of ECR systems, including photo-anode-assisted ECR systems and bio-anode-assisted ECR systems, are explained in detail. Additionally, the cathodic reaction mechanisms and pathways of ECR are described along with a discussion of different design strategies for cathode catalysts to enhance conversion efficiency and selectivity. The emerging challenges and some perspective on both anode materials and cathodic catalysts are also outlined for better development of ECR systems.     

InBi Bimetallic Sites for Efficient Electrochemical Reduction of CO2 to HCOOH

Formic acid is receiving intensive attention as being one of the most progressive chemical fuels for the electrochemical reduction of carbon dioxide. However, the majority of catalysts suffer from low current density and Faraday efficiency. To this end, an efficient catalyst of In/Bi-750 with InO_x nanodots load is prepared on a two-dimensional nanoflake Bi₂O₂CO₃ substrate, which increases the adsorption of ^*CO₂ due to the synergistic interaction between the bimetals and the exposure of sufficient active sites. In the H-type electrolytic cell, the formate Faraday efficiency (FE) reaches 97.17% at –1.0 V (vs reversible hydrogen electrode (RHE)) with no significant decay over 48 h. A formate Faraday efficiency of 90.83% is also obtained in the flow cell at a higher current density of 200 mA cm⁻². Both in-situ Fourier transform infrared spectroscopy (FT-IR) and theoretical calculations show that the BiIn bimetallic site can deliver superior binding energy to the ^*OCHO intermediate, thereby fundamentally accelerating the conversion of CO₂ to HCOOH. Furthermore, assembled Zn-CO₂ cell exhibits a maximum power of 6.97 mW cm⁻¹ and a stability of 60 h.