Engineering nanostructures of CuO-based photocatalysts for water treatment: Current progress and future challenges

Nowadays, increasing extortions regarding environmental problems and energy scarcity have stuck the development and endurance of human society. The issue of inorganic and organic pollutants that exist in water from agricultural, domestic, and industrial activities has directed the development of advanced technologies to address the challenges of water scarcity efficiently. To solve this major issue, various scientists and researchers are looking for novel and effective technologies that can efficiently remove pollutants from wastewater. Nanoscale metal oxide materials have been proposed due to their distinctive size, physical and chemical properties along with promising applications. Cupric Oxide (CuO) is one of the most commonly used benchmark photocatalysts in photodegradation owing to the fact that they are cost-effective, non-toxic, and more efficient in absorption across a significant fraction of solar spectrum. In this review, we have summarized synthetic strategies of CuO fabrication, modification methods with applications for water treatment purposes. Moreover, an elaborative discussion on feasible strategies includes; binary and ternary heterojunction formation, Z-scheme based photocatalytic system, incorporation of rare earth/transition metal ions as dopants, and carbonaceous materials serving as a support system. The mechanistic insight inferring photo-induced charge separation and transfer, the functional reactive radical species involved in a photocatalytic reaction, have been successfully featured and examined. Finally, a conclusive remark regarding current studies and unresolved challenges related to CuO are put forth for future perspectives.     

铜在空气中生成碱式碳酸铜的热力学分析

从热力学角度研究了酸度、湿度、水的存在状态不同时,单质铜在空气中生成碱式碳酸铜的电动势及其自由能变。通过计算发现:在酸性条件下,p H的大小对于反应的自发性没有影响;大气中二氧化碳溶解达到饱和时,空气湿度增加,反应的自发性略微增加;相同条件下,水由气态变为液态时,反应的自发性增幅较大。     

One‐pot Synthesis of 3,4‐Dihydropyrimidin‐2(1H)‐ones Catalysed by Cupric Acetate under Solvent‐free Conditions

A solvent‐free synthesis of 3,4‐dihydropyrimidin‐2(1H)‐ones from aromatic aldehydes, β‐keto ester/acetyl acetone and urea catalysed by cupric acetate under thermal condition is reported as a simple and an efficient protocol. Compared with classical Biginelli reaction reported in 1893, this new method provides much improved modification in terms of yield and reaction time. The usage of milder catalyst, environmental friendly procedures and excellent yields within a very short time (5–15 min) are the advantages of the method in which the involvement of solvent‐free condition adds an edge to the method. Thus, the efficiency of the protocol enabled the rapid synthesis of 3,4‐dihydropyrimidin‐2(1H)‐one derivatives in a short duration.     

Effect of Ultrasonic‐assisted Preparation Methods on Structure,Morphology and Optical Properties of Nanosized Cupric Oxide

Cupric oxide is a p‐type semiconductor with a narrow band‐gap which is suitable for catalysis, electrochemical cells, field emission devices and gas sensor applications. Despite considerable efforts devoted to the preparation of the nanosized CuO, there is a lack of information about ultrasonic‐assisted (US) preparation methods. Nanosized cupric oxide was successfully prepared through different ultrasonic‐assisted (US) preparation methods. Furthermore, the influence of preparation method on the structure, morphology and optical properties of nanosized CuO has been reported. XRD patterns were identical to the single‐phase pure CuO with a monoclinic structure. The enhancement of the crystallinity and crystallite size was observed for the sample prepared through the US thermal decomposition. The absorption band of CuO nanocrystals prepared through the US liquid hydrolysis shows a clear red shift of about 40 nm compared to those obtained with other preparation methods. Our results indicated that almost spherical CuO nanoparticles with an average size of 65 nm were prepared during the US thermal decomposition, while CuO rod‐like nanostructures with an average diameter of about 16 nm were obtained via the US liquid hydrolysis method. The band gap values of nanosized CuO samples were larger than the reported value for the bulk CuO. Synthesized CuO samples by US methods with adjustable and controllable properties make the applicability of cupric oxide even more versatile.     

Highly photocatalytic activity of metallic hydroxide/titanium dioxide nanoparticles prepared via a modified wet precipitation process

Surface modification is one important approach to increase the photocatalytic activity of TiO₂. By using a modified wet precipitation process, novel M(OH)_x/TiO₂ nanoparticles were synthesized, where M(OH)_x represents ferric or cupric hydroxide. The prepared M(OH)_x/TiO₂ powders were characterized with XRD, FT-IR, BET, UV–vis DRS, and TGA, and were observed to yield high photocatalytic ability by using methyl orange (MO) as a model compound of organic pollutants to be degraded. Due to the accelerating effects of the new photocatalyst, the half-time of MO during its photocatalytic degradation at pH 6.0 over M(OH)_x/TiO₂ was decreased from 332 min for unmodified neat TiO₂ to 63 min for Fe(OH)₃/TiO₂ and 65 min for Cu(OH)₂/TiO₂, respectively. The enhancing effects of M(OH)_x/TiO₂ was further observed in a wide composition range with various M/Ti atomic ratios in the photocatalysts and in a wide pH range of the MO solution from 3 to 7. This enhancing effect is mainly attributed to the increased trapping of the photogenerated electron by the higher valence sites (Fe(III) or Cu(II)) in the hydroxide layer near the M(OH)_x/TiO₂ interface and the enriched surface hydroxyl groups which accept photogenerated holes to yield more hydroxyl radicals.     

CuO/ZnO/Al2O3合成甲醇催化剂制备方法

ＣｕＯ／ＺｎＯ／Ａｌ２Ｏ３合成甲醇催化剂的制备方法吴晓晖刘金尧刘崇微朱起明（清华大学化学系一碳化工国家重点实验室，北京１０００８４）何菲（天津大学化工系一碳化工国家重点实验室，天津３０００７２）关键词氧化铜，氧化锌，氧化铝，超细粒子，草酸盐胶体...     

硫氰酸铵-罗丹明 B-H2O的液-固体系浮选分离铜(Ⅱ)的研究

研究了硫酸铵存在下硫氰酸铵-罗丹明B-H2O的液-固体系浮选分离铜(Ⅱ)的行为及其与常见离子分离的条件.结果表明,当(NH4)2SO4用量为1.0 g,0.1 mol·L-1硫氰酸铵溶液1.5 mL和0.001 mol·L-1罗丹明B溶液2.0 mL时,铜(Ⅱ)以不溶于水的三元离子缔合物(RhB)2[Cu(SCN)4]形式在液-固两相界面定量浮选析出,而Cdd2、Mn2+、Co2+、Ni2+、Al3+等离子在此条件下不被浮选,实现了铜(Ⅱ)与这些离子的定量分离,对合成水样中微量铜(Ⅱ)进行的定量浮选分离测定,浮选富集的平均回收率达101.4%.     

巯基丁二胺铜单层修饰金电极上HIV-p24抗原的电化学免疫检测

制备了用巯基丁二胺铜(CuL)修饰的金电极并用作HIV-p24抗原蛋白(简称p24)免疫检测的化学传感器。CuL通过单层自组装固定在金电极表面,其覆盖率为1.02×10-11mol.cm-2,在含有1.0 mmol.L-1过氧化氢并在pH 6.2的磷酸盐缓冲溶液中,制备的校正曲线的线性范围为0.5-150μg.L-1p24对相应的伏安响应,方法的检出限为0.2μg.L-1。在10μg.L-1p24浓度水平作精密度试验,得RSD值为3.5%,于试样中分别加入5,15,20及30μg.L-1p24进行回收率试验,所得结果在98%-102%之间。此方法毋需另加电子传递媒介体。应用此方法于临床血清分析,所得结果与放射性免疫法的结果一致,且所得RSD值均小于0.3%。     

高效抗菌Cu2+-壳聚糖季铵盐/丙烯酸复合物的制备

以过硫酸铵为引发剂,在壳聚糖季铵盐（HACC）上接枝丙烯酸（AAc）并络合Cu²⁺,制备了具有高效抗菌性能的HACC-g-PAAc-Cu²⁺复合物.采用红外光谱（FTIR）和核磁共振波谱（¹H NMR）表征了壳聚糖季铵盐接枝改性前后的化学结构变化;利用紫外-可见吸收光谱（UV-Vis）、Cu²⁺选择电极和热失重分析（TGA）表征了壳聚糖季铵盐接枝前后负载Cu²⁺的能力;测定了HACC-Cu²⁺和HACC-g-PAAc-Cu²⁺对金黄色葡萄球菌及大肠杆菌的最小抑菌浓度,并对小鼠经口摄入毒性和兔皮肤敷涂刺激性进行了考察.研究结果表明,在壳聚糖季铵盐上负载Cu²⁺能够有效提高其抗菌性;接枝丙烯酸能提高HACC负载Cu²⁺的能力和抗菌性,Cu/HACC结构单元的摩尔比由接枝前的3：7提高到接枝后的1：1;对金黄色葡萄球菌的最小抑菌浓度由60 mg/L下降到9.2 mg/L,对大肠杆菌的最小抑菌浓度由37 mg/L下降到6.3 mg/L,无摄入毒性和皮肤刺激性.     

共沉淀分离富集-ICP-AES测定饲料级硫酸铜中微量As和Pb

在氨性介质中 ,以硫酸铁铵作共沉淀剂 ,预富集硫酸铜中的微量砷、铅 ,ICP- AES测定砷、铅的含量。方法检出限可满足日常分析的需要。加标回收率 As95 .0 %— 98.8% ;Pb96 .9%— 97.5 % ;相对标准偏差As4 .4 % ;Pb5 .8%。