阿布力克木·阿布力孜

Facile fabrication of SnO₂ modified hierarchical BiOI S-scheme heterojunction photocatalyst with efficient activity for carbon dioxide reduction

In this paper, a series of SnO₂-modified BiOI (SnO₂/BiOI) novel s-scheme heterojunction microsphere catalysts were synthesized, and the effect of temperature on the photocatalytic CO₂ reduction reactivity of SnO₂ grown on pure BiOI surface was systematically investigated by adjusting the calcination reaction temperature. Among all SnO₂/BiOI composite photocatalytic systems, the highest CH₃OH yield (1183 μmol/g_cat, 4 h) was achieved when SnO₂/BiOI was synthesized at 400 °C, which was 2.7 times higher than that of BiOI alone (437 μmol/g_cat, 4 h). The SnO₂/BiOI microspheres with s-scheme heterojunction exhibited surprising photocatalytic performance for CH₃OH formation due to the formation of an internal eletricfield between SnO₂ and BiOI also facilitated the separation of the photogenerated electron-hole pairs.

本文合成了一系列SnO₂修饰BiOI（SnO₂/BiOI）新型s型异质结微球催化剂，系统地研究了温度对纯BiOI表面生长的SnO₂光催化CO₂还原反应活性的影响。通过调节焙烧反应温度进行研究。在所有SnO₂/BiOI 复合光催化体系中，在 400℃ 下合成 SnO₂/BiOI 时 CH₃OH 产率最高（1183 μmol/g_cat，4 h），是单独合成 BiOI 时（437 μmol/g_cat，4h）的2.7倍。具有S型异质结的 SnO₂/BiOI 微球在生成 CH₃OH 时表现出令人惊讶的光催化性能，这是因为 SnO₂ 和 BiOI 之间形成了内部电场，也促进了光生电子-空穴对的分离。

DOI: 10.1016/j.jiec.2023.05.041

In-situ growth Cu₂O on C–BiOI to fabrication p-p heterojunction with enhanced visible-light reduction of CO₂

In this study, novel homotypic (p-p) heterojunctions based on the coupling of Cu₂O and C–BiOI were synthesized under mild conditions using a two-step method. The microscopic morphology, optical, photoelectrochemical, and photocatalytic properties of the synthesized samples were investigated. The catalytic properties of the samples were also investigated by photocatalytic CO₂ reduction. The results showed that Cu₂O_30%@C₃–BiOI exhibited the best photocatalytic performance when the molar ratio of C to Bi was 1:15 and the loading of Cu₂O was 30%, and the yields of methanol and ethanol from CO₂ within 8 h were 722.88 μmol/g_cat and 264.46 μmol/g_cat, respectively. In addition, the introduction of C improved the light absorption of BiOI, and the introduction of Cu₂O effectively improved the migration and separation efficiency of photogenerated carriers. The results of DRS, photocurrent, PL, and EIS proved the photocatalytic reaction mechanism.

本研究采用两步法，在温和条件下合成了基于 Cu₂O 和 C-BiOI 耦合的新型同型 (p-p) 异质结。研究了合成样品的微观形貌、光学、光电化学和光催化性能。还通过光催化二氧化碳还原法研究了样品的催化特性。结果表明，当 C 与 Bi 的摩尔比为 1:15、Cu₂O 的负载量为 30% 时，Cu₂O_30%@C₃-BiOI 的光催化性能最佳，8 h 内从 CO₂ 中分离出甲醇和乙醇的产率分别为 722.88 μmol/g_cat 和 264.46 μmol/g_cat。此外，C 的引入改善了 BiOI 的光吸收，Cu₂O 的引入有效提高了光生载流子的迁移和分离效率。DRS、光电流、PL 和 EIS 的结果证明了光催化反应机理。

DOI： 10.1016/j.optmat.2023.113790

Process optimization of esterification for deacidification in waste cooking oil: RSM approach and for biodiesel production assisted with ultrasonic and solvent

This study investigated the use of waste cooking oil, as a raw material for biodiesel production, solves its treatment problem, and provides additional value. The low acid value is achieved by the esterification process with H₂SO₄ as a catalyst for deacidification of FFAs which was optimized using response surface design to invest the effect of the operating parameters in this work. The effects of reaction time, catalyst concentration, temperature, and the molar ratio of methanol to oil on the deacidification were analyzed by the regression model equation in detail. The optimum conditions of the ratio of methanol to oil ratio (8), H₂SO₄ catalysis concentration (5 wt%), reaction temperature (60℃), and reaction time (108 min) were obtained and an acid value of 0.42 was achieved. The pre-esterified oil was used to produce biodiesel through transesterification with ultrasonic and solvent, and 98.5% FAME yield was achieved under the optimal condition that catalyst dosage of 2 wt%, the molar ratio of oil to methanol of 1:6, reaction temperature of 40℃, solvent type of n-hexane, the solvent dosage of 8: 1, pulse time of 7 s on/1s off, and ultrasonic power of 130 W. Therefore, this study clearly showed the necessity of pre-esterification of WCO as raw material, and assisted measures of ultrasound and co-solvent for biodiesel production, which is more efficient, less time-consuming, and more helpful than the usual process because it reduces the optimal conditions needed to achieve high FAME% yield.

本研究调查了废弃食用油作为生物柴油生产原料的用途，解决了其处理问题，并提供了附加价值。通过使用 H₂SO₄作为 FFA 脱酸催化剂的酯化过程实现了低酸值，该过程使用响应面设计进行了优化，以投资本工作中操作参数的影响。通过回归模型方程详细分析了反应时间、催化剂浓度、温度、甲醇油摩尔比对脱酸的影响。甲醇油比(8)、H₂SO₄的最佳条件得到催化浓度（5 wt%）、反应温度（60℃）和反应时间（108 min），酸值为0.42。将预酯化油通过超声波和溶剂进行酯交换生产生物柴油，在催化剂用量为2 wt%、油与甲醇的摩尔比为1:6、反应温度为最佳条件下，FAME收率达到98.5%。 40℃，溶剂型n-己烷，溶剂用量8:1，脉冲时间7s开/1s关，超声波功率130W。因此，本研究明确表明以WCO为原料进行预酯化的必要性，辅助措施用于生物柴油生产的超声波和助溶剂，它比通常的工艺更有效、更省时、更有帮助，因为它减少了实现高 FAME% 产率所需的最佳条件。

DOI: 10.1016/j.fuel.2022.123697

Sonochemical Fabrication of s-Scheme Hierarchical CdS/BiOBr Heterojunction Photocatalyst with High Performance for Carbon Dioxide Reduction

In this study, a series of CdS-modified BiOBr (CdS/BiOBr) microspheres are fabricated by mild hydrolysis-ultrasonic method and the effect of CdS growing on the photocatalytic CO₂ reduction activities of BiOBr are systematically investigated. Among all CdS/BiOBr composite photocatalysis, the highest value of CH₃OH yields (876 µmolg_cat⁻¹, 4 h) is achieved with 15% CdS/BiOBr, which is nearly double higher than alone BiOBr (435 µmolg_cat⁻¹). Comparatively, the CdS/BiOBr microspheres with s-scheme heterostructure exhibit the surprising photocatalytic performance and CH₃OH selectivity, which are attributed to the enhanced light absorption, as well as effective separation and migration of the photoinduced electron–hole pairs induced by the s-scheme heterojunction between BiOBr and CdS. This study provides a mild hydrolysis-ultrasonic method for environmental remediation and converting energy using cost-effective semiconductor materials.

本研究采用温和水解-超声法制备了一系列 CdS 改性 BiOBr（CdS/BiOBr）微球，并系统研究了 CdS 生长对 BiOBr 光催化 CO₂ 还原活性的影响。在所有 CdS/BiOBr 复合光催化技术中，15% CdS/BiOBr 的 CH3OH 产率（876 µmolg_cat⁻¹, 4 h）最高，比单独使用 BiOBr（435 µmolg_cat⁻¹ ）高出近一倍。相比之下，具有 s 型异质结构的 CdS/BiOBr 微球表现出令人惊讶的光催化性能和对 CH₃OH 的选择性，这归因于 BiOBr 和 CdS 之间的 s 型异质结增强了光吸收以及光诱导电子-空穴对的有效分离和迁移。

DOI：10.1002/ppsc.202200019

In situ self-assembled S-scheme BiOBr/pCN hybrid with enhanced photocatalytic activity for organic pollutant degradation and CO₂ reduction

英文简介：In this work, hollow hierarchical BiOBr microspheres were immobilized on the surface of protonated g-C₃N₄ (pCN) to form a unique S-scheme heterostructure via an in situ hydrothermal method. The synthesized samples exhibited remarkable photocatalytic activity for the degradation of rhodamine B (RhB) and the reduction of CO₂ to methanol. The characterization results indicate that pCN is an effective support for hollow hierarchical BiOBr by enhancing the adsorption and transformation capability for RhB and CO₂ molecules, and it improves the separation of photogenerated charge carriers by forming a Schottky barrier. Additionally, the introduction of pCN affected the morphology of BiOBr and provided a larger specific surface area. Hence, the pCN/BiOBr hybrid showed remarkably improved degradation of RhB and reduction of CO₂ under visible-light irradiation. Specially, the 10% pCN/BiOBr hybrid had the best photocatalytic activity for RhB degradation (95.23%, 30 min) and CO₂ reduction (1068.07 μmol/g_cat, 4 h), which was approximately 1.70-fold and 2.56-fold, respectively, that of BiOBr. A possible S-scheme electron transform pattern is proposed to explain the photocatalytic mechanism of the 10% pCN/BiOBr hybrid.

在这项工作中，空心的BiBir空心微球固定在质子化的gC₃N₄（pCN）的表面上，通过原位水热法形成独特的S型异质结构。合成的样品对罗丹明B（RhB）的降解和CO₂还原为甲醇具有显着的光催化活性。表征结果表明，pCN通过增强对RhB和CO₂的吸附和转化能力，是对空心分级BiOBr的有效支持。分子，并通过形成肖特基势垒来改善光生载流子的分离。另外，pCN的引入影响了BiOBr的形态，并提供了更大的比表面积。因此，在可见光照射下，pCN/BiOBr杂化物显示出RhB的降解显着改善和CO₂减少。特别地，10％pCN / BiOBr杂合体对RhB降解（95.23％，30分钟）和CO₂还原（1068.07μmol/g_cat，4 h）具有最佳的光催化活性，分别约为1.70倍和2.56倍，分别是BiOBr。提出了一种可能的S方案电子转化模式来解释10％pCN/BiOBr杂化体的光催化机理。

DOI： 10.1016/j.apsusc.2021.149828

In-situ fabrication of hollow BiOI_xCl_y n-n type heterojunction microspheres with enhanced visible-light-driven performance for rhodamine B degradation and CO₂ reduction

In this work, in situ self-assembled hollow BiOI_xCl_y n-n type heterojunction microspheres were simply synthesized via a one-step hydrothermal method, and the microstructure, morphology, optical, photoelectrochemical, and photocatalytic properties of the samples were researched. The photocatalytic activity of materials was investigated for Rhodamine B (RhB) degradation and CO₂ reduction. The characterization results illustrated that the introduction of moderate amounts of Cl− in BiOI could promote the conversion of RhB and CO₂, and it improved separation efficiency of photogenerated electrons and holes in BiOI. Specially, when the doping ratio of I⁻ and Cl⁻ was 2:1, BiOI^xCl^y exhibited the most outstanding photocatalytic activity for RhB degradation (99.42 %, 20 min) and reduction of CO₂ to methanol (1042.12 µmol/g_cat, 8 h) and ethanol (264.53 µmol/g_cat, 8 h), which were approximately 3.40 and 3.91times larger than that of BiOI, respectively. This study could describe a potential strategy for assisting with environmental purification and energy transformation.

本工作采用一步水热法简单地合成了原位自组装空心BiOI_xCl_y n-n型异质结微球，并研究了样品的微观结构、形貌、光学、光电化学和光催化性能。研究了材料对罗丹明 B (RhB) 降解和 CO₂还原的光催化活性。表征结果表明，在BiOI中引入适量的Cl^-可以促进RhB和CO²的转化, 并提高了 BiOI 中光生电子和空穴的分离效率。特别地，当 I^-和 Cl^-的掺杂比为 2:1 时，BiOI_xCl_y表现出最出色的光催化活性，用于降解 RhB（99.42 %，20 分钟）和将 CO₂还原为甲醇（1042.12 µmol/g_cat, 8 h) 和乙醇 (264.53 µmol/g_cat, 8 h)，分别比 BiOI 大 3.40 倍和 3.91 倍。这项研究可以描述协助环境净化和能源转型的潜在策略。

DOI：10.1016/j.jiec.2022.10.040

Z-type heterojunction of graphene quantum dots/g-C₃N₄/BiOCl with excellent photocatalytic performance for nit

Here we report a novel g-C₃N₄ /BiOBr-RGO aerogel ternary-component heterojunction photocatalyst for degradation of RhB under visible light irradiation. As a result of synergistic effect of the g-C₃N₄, BiOBr and RGO, the hybrid photocatalysts exhibit better activity than the single component catalysts (pure g-C₃N₄, BiOBr) and bi-component catalysts (g-C₃N₄/BiOBr) in the same time period (60 min). The enhanced photocatalytic performance originates from a novel nanoarchitecture in which BiOBr exposed more active plane and RGO worked as a conductive support further improved the photogenerated charge separation. Moreover, due to the 3D structure of RGO after reaction the photocatalysts can be easily removed from the treated solution and reused, which opens up a way for the recycling applications of catalysts in aqueous reaction systems.

在这里，我们报告了一种新型 g-C₃N₄ /BiOBr-RGO 气凝胶三元异质结光催化剂，用于在可见光照射下降解 RhB。由于g-C₃N₄、BiOBr 和RGO 的协同作用，混合光催化剂表现出比单组分催化剂（纯g-C₃N₄、BiOBr）和双组分催化剂（g-C₃N₄/BiOBr）更好的活性在同一时间段内（60 分钟）。增强的光催化性能源于一种新型纳米结构，其中 BiOBr 暴露出更多的活性平面，RGO 作为导电载体进一步改善了光生电荷分离。此外，由于反应后 RGO 的 3D 结构，光催化剂可以很容易地从处理过的溶液中去除并重复使用，这为催化剂在水性反应体系中的回收应用开辟了道路。

DOI：10.1016/j.jallcom.2017.09.175

Surfactant-enhanced ZnO_x/CaO catalytic activity for ultrasound-assisted biodiesel production from waste cooking oil

In this work, ZnO_x/CaO non-homogeneous catalysts were synthesized through a urea-precipitation calcination method for the transesterification of WCO as feedstock. The optimal Zn : Ca mass ratio was 0.2. The effect of the morphological structure of the catalyst to the biodiesel yield was investigated using different levels of surfactants. The crystalline shape, microstructure and elemental state of catalysts were investigated using XRD analysis, SEM and XPS. Ultrasonication was used to accelerate transesterification reactions. The highest biodiesel yield (97.6%) was achieved under an alcohol : oil molar ratio of 12 : 1, 2 wt% of catalyst loading, temperature of 65 °C, reaction duration of 40 min, 130 W of ultrasonic power and ultrasonic pulse mode of 5 s on and 1 s off. The synthesized biodiesel was analyzed further using spectroscopy (FT-IR and 1H-NMR). Cycling experiments of catalysts and XRD analysis of used catalysts demonstrated the excellent stability of the polyvinylpyrrolidone-critic acid-treated ZnO_0.2/CaO catalysts. This study can provide guidance for the construction of high-performance non-homogeneous catalysts for biodiesel production. This strategy could have a beneficial impact on the environmentally friendly production of biodiesels and control of environmental pollution.

本工作以WCO为原料，采用尿素沉淀煅烧法合成了ZnO_x/CaO非均相催化剂，用于酯交换反应。最佳Zn:Ca质量比为0.2。使用不同水平的表面活性剂研究了催化剂的形态结构对生物柴油产率的影响。利用 XRD 分析、SEM 和 XPS 研究了催化剂的晶形、微观结构和元素状态。使用超声波加速酯交换反应。在醇:油摩尔比为12:1、催化剂负载量为2 wt.%、温度为65℃、反应时间为40分钟、超声波功率为130W、超声波脉冲模式下，生物柴油收率最高（97.6%）。 5 秒开启，1 秒关闭。使用光谱（FT-IR 和1 H-NMR）进一步分析合成的生物柴油。催化剂的循环实验和用过的催化剂的X射线衍射分析表明，聚乙烯吡咯烷酮-临界酸处理的ZnO_0.2/CaO催化剂具有优异的稳定性。该研究可为构建用于生物柴油生产的高性能非均相催化剂提供指导。该策略可能对生物柴油的环保生产和环境污染控制产生有益影响。

DOI：10.1039/d3re00306j