Carbon nanoparticles as visible-light photocatalysts for efficient CO2 conversion and beyond

Increasing atmospheric CO(2) levels have generated much concern, driving the ongoing carbon sequestration effort. A compelling CO(2) sequestration option is its photocatalytic conversion to hydrocarbons, for which the use of solar irradiation represents an ultimate solution. Here we report a new strategy of using surface-functionalized small carbon nanoparticles to harvest visible photons for subsequent charge separation on the particle surface in order to drive the efficient photocatalytic process. The aqueous solubility of the catalysts enables photoreduction under more desirable homogeneous reaction conditions. Beyond CO(2) conversion, the nanoscale carbon-based photocatalysts are also useful for the photogeneration of H(2) from water under similar conditions.     

One-step synthesis of ultra-small amount of Pd-Alloyed Zinc Nanosheets for efficient electrochemical CO2 reduction to CO

The practicality of the electrochemical CO₂ reduction technique depends on the development of cost-effective, robust, and highly selective catalysts. To achieve this goal, we have engineered self-supported 3D electrodes composed of Pd-Zn nanosheets (NSs) for CO₂ electrochemical reduction to CO with minimal Pd content. This innovative electrode with an increased surface area was created using an electrodeposition method employing a dynamic hydrogen bubble template. By precisely adjusting the Pd content, we improved the thickness, porosity, and surface area of the electrodes, resulting in a CO₂-to-CO selectivity reaching as high as 88.5 %, with an average of at least 80 % sustained over 10 hours. This remarkable improved activity can be attributed to the synergistic effects of an appropriate Pd/Zn atomic ratio as well as to the large surface area of nanosheets structures with rich edge active sites. Furthermore, to get around the limitations of CO₂ mass transfer, reactions were done at high pressures conditions ranging from 3 to 9.5 bar; this strategic approach yielded an outstanding partial current density of −304.6 mA cm⁻² for CO. These noteworthy findings establish concepts for constructing effective and earth-abundant CO-producing electrocatalysts.     

Electrochemical synthesis of sulfur-doped graphene sheets for highly efficient oxygen reduction

Sulfur(S)-doped graphene sheets were prepared by a facile electrochemical method, which effectively combined exfoliation of graphite and in situ S doping of graphene together. The metal-free S-doped graphene sheets exhibit high electrocatalytic activity, long-term stability, and excellent tolerance to cross-over effects of methanol in alkaline media for the oxygen reduction reaction(ORR), indicating that these S-doped graphene sheets possess great potential for a substitute for Pt-based catalysts in fuel cells.     

A new polypyridyl-based Ru (II) complex as a highly efficient electrocatalyst for CO2 reduction

A new polypyridyl Ru (II) complex, cis-[Ru (Me₄phen)₂(CH₃CN)₂](NO₃)₂ (Me₄phen = 3,4,7,8-tetramethyl-1,10-phenanthroline) has been prepared and fully characterized by elemental analysis, X-ray crystallography, cyclic voltammetry and spectroscopic techniques. The solid-state structure of the complex indicated that the Ru (II) center is sitting in an N₄N′₂ coordination environment with a distorted octahedral geometry. Cyclic voltammetry technique was used to investigate the catalytic activity of the Ru (II) complex on the electrocatalytic reduction of CO₂ to CO in acetonitrile. The effect of the different reaction parameters, including the scan rate, concentration of the electrocatalyst [complex Ru (II)] and reaction temperature, on the catalytic activity was also investigated. The results showed that the electrocatalytic activity of the complex increases with increasing electrocatalyst concentration and scan rate. Further, the CO₂ reduction peak current decreases at lower temperatures owing to the inverse relationship between the temperature and activation energy. The theoretical calculations confirmed the proposed electrocatalytic mechanism comprising seven steps.     

Constructing low-valent Ni nanoparticles for highly selective CO2 reduction

The electroreduction of CO₂（CO₂RR） into value-added chemicals is a sustainable strategy for mitigating global warming and managing the global carbon balance. However, developing an efficient and selective catalyst is still the central challenge. Here, we developed a simple two-step pyrolysis method to confine low-valent Ni-based nanoparticles within nitrogen-doped carbon（Ni-NC）. As a result, such Ni-based nanoparticles can effectively reduce CO₂ to CO, with a max...     

Selected-control synthesis of metal phosphonate nanoparticles and nanorods

By surfactant-assisted methods, nanoscale Co(O3PC6H5).H2O species of different morphologies, namely, nanoparticles and nanorods, have been successfully synthesized and characterized. Upon removal of the organic part of the compound, peculiar Co2P2O7 porous nanorods formed.     

Ultrathin two-dimensional metal-organic framework nanosheets for efficient electrochemical CO2 reduction

Electrochemical CO2 reduction into CO or high-value products is regarded as a feasible pathway for energy conversion, which has attracted universal attention in...     

Electrochemical CO2 reduction with earth-abundant metal catalysts

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Development of efficient photocatalytic systems for CO2 reduction using mononuclear and multinuclear metal complexes based on mechanistic studies

Photocatalytic systems for CO₂ reduction using metal complexes, especially rhenium(I) complexes as a main component, are reviewed: mononuclear Re(I) complexes, mixed systems with two different Re(I) complexes, and supramolecule systems with a Re(I) complex connected to a ruthenium(II) complex. We focus on the mechanistic studies and the architecture for constructing the photocatalytic systems based on the mechanism.     

Cloride-derived copper electrode for efficient electrochemical reduction of CO2 to ethylene

Transformation of CuCl into cubic structure of bi-phasic Cu₂O-Cu (CB-Cu) enhanced production of ethylene from electrochemical reduction of CO₂.     

Hybrid porous tin(IV) phosphonate: an efficient catalyst for adipic acid synthesis and a very good adsorbent for CO2 uptake

A new porous organic-inorganic hybrid tin phosphonate material has been synthesized hydrothermally, which shows a Brunauer-Emmett-Teller surface area of 723 m(2) g(-1) and it adsorbs 4.8 mmol g(-1) CO(2) at 273 K and 5 bar pressure. The material also shows remarkable catalytic activity in one-pot liquid phase oxidation of cyclohexanone to adipic acid under eco-friendly conditions.     

General approach for the synthesis of organic-inorganic hybrid nanoparticles mediated by supercritical CO2

We report in this paper novel chemistry that addresses the problem of surfactant solubility in supercritical CO2 for metal nanoparticle synthesis. This new approach for the preparation of organic-functionalized inorganic nanoparticles relies on the reduction of a metal precursor in a CO2-containing insoluble polymer. Reduction of the metal with H2 leads to small nanocrystals stabilized by the polymer with a relatively small polydispersity. The functionalized metal nanoparticles are recovered as a dry powder, free of any organic solvents, which can then be resuspended in an appropriate solvent. This approach limits the number of steps for the preparation of functional nanoparticles which are ready for use. To illustrate this, we report results of the preparation of palladium and silver nanoparticles of 3-5 nm size stabilized with hyperbranched polyamines, functionalized with perfluoroalkyl, perfluorooligoether, non-fluorinated alkyl, polysiloxane, or polyethylene glycol moieties.     

在光催化还原CO2中具有高催化效率的八面体Cu2O修饰的TiO2纳米管

光催化还原CO2生成烃类燃料是一种可同时解决全球变暖和能源危机问题的最有效途径之一。尽管这方面的研究已经取得了一定的进展,但是整体的光催化转换效率还非常低。因此,需要发展更加高效的催化剂。由于半导体材料禁带宽度与太阳光谱相匹配,人们已经对其进行了广泛研究。其中TiO2因具有无毒、强氧化性以及良好的光学和电学性质等而成为最主要的研究对象。但是对于光催化还原CO2反应来说, TiO2仍存在很多不足,如只能吸收太阳光谱中的紫外光,光生载流子会快速结合,以及光生空穴的强氧化能力等,这些都限制了其光催化还原CO2的效率。采用窄禁带宽度半导体修饰TiO2是解决上述不足的有效途径之一。本文采用简单的电化学方法成功制备了一种由窄禁带半导体Cu2O修饰的TiO2纳米管(TNTs)的复合物,并运用扫描电子显微镜(SEM)、X射线衍射(XRD)以及X射线光电子能谱(XPS)表征了所制备复合物的形貌、化学组成和结晶度。表征结果显示,所制备的TiO2为整齐排列的纳米管阵列结构;复合物中的纳米颗粒为Cu2O;当电化学沉积Cu2O的时间为5 min时,得到的Cu2O纳米颗粒初步呈类八面体结构。随着沉积时间的增加, Cu2O颗粒尺寸增加,具有八面体结构。 XRD和XPS结果表明, TiO2纳米管为锐钛矿,八面体Cu2O纳米颗粒的主要暴露晶面为(111)面。我们还进一步研究了不同量Cu2O纳米颗粒修饰的TiO2纳米管复合物在可见光以及模拟太阳光下光催化还原CO2的能力。在可见光下,由于自身的禁带宽度,纯净的TiO2纳米管没有任何光催化还原CO2的能力;经过Cu2O纳米颗粒的修饰,复合物显现出明显的光催化还原CO2的能力,其中经过30 min Cu2O沉积的TNTs具有最高的光催化效率。在模拟太阳光下,经过15 min Cu2O沉积的TNTs具有最高的光催化效率。在所有光催化还原CO2过程中,主要碳氢产物为甲烷。为了深入地理解该复合体系在还原CO2中的高催化效率,我们对催化剂进行了进一步的表征。紫外-可见漫反射光谱表明, Cu2O八面体纳米颗粒的沉积将TNTs的吸收光谱拓展到了可见光区域,提高了复合物对太阳光的吸收能力。此外,我们还通过测试所制样品的光电流反应、荧光发射光谱以及电化学阻抗谱,研究了催化剂中光生电子和空穴的分离和迁移能力。结果表明,适量的Cu2O沉积提高了复合物对光的吸收能力,增加了光生载流子的数量,从而使更多的光生载流子参与光催化反应。综上,本文首次报道了八面体Cu2O纳米颗粒修饰TNTs复合物的光催化还原CO2的能力。在一定量的Cu2O纳米颗粒修饰下,该复合物在光催化还原CO2生成烃类反应中表现出高效性。经过一系列详细的表征和讨论,我们认为其高效性主要源于三个方面：(1) TNTs的管状结构为反应物的吸附提供了大量的活性位点,同时一维的管状结构更有利于光生载流子的运载,从而提高了电子和空穴的分离;(2) Cu2O纳米颗粒的修饰提高了催化剂对光的吸收,促进催化剂最大程度地利用太阳光;(3) TiO2和Cu2O之间导带以及价带位置的匹配,在减少光生载流子复合的同时也降低了TiO2价带上空穴的氧化能力,从而抑制了CO2还原产物的再氧化过程。     

A series of highly efficient photocatalysts for organic contaminants degradation under visible light irradiation

Antimonic acid and N-doped antimonic acid, solid acids with d(10) electron configuration, are reported as novel photocatalysts for rhodamine B (RhB) degradation under visible light irradiation. They show much higher activities in comparison with P25 and photolysis. However, the extent of degradation abilities for RhB was not consistent with the formation rate of the active ˙OH radicals under visible light irradiation.     

Metal-organic frameworks MOF-808-X as highly efficient catalysts for direct synthesis of dimethyl carbonate from CO2 and methanol

A series of metal-organic frameworks MOF-808-X (6-connected) were synthesized by regulating the ZrOCl₂·8H₂O/1,3,5-benzenetricarboxylic acid (BTC) molar ratio (X) and tested for the direct synthesis of dimethyl carbonate (DMC) from CO₂ and CH₃OH with 1,1,1-trimethoxymethane (TMM) as a dehydrating agent. The effect of the ZrOCl₂·8H₂O/BTC molar ratio on the physicochemical properties and catalytic performance of MOF-808-X was investigated. Results showed that a proper ZrOCl₂·8H₂O/BTC molar ratio during MOF-808-X synthesis was fairly important to reduce the redundant BTC or zirconium clusters trapped in the micropores of MOF-808-X. MOF-808-4, with almost no redundant BTC or zirconium clusters trapped in the micropores, exhibited the largest surface area, micropore size, and the number of acidic-basic sites, and consequently showed the best activity among all MOF-808-X, with the highest DMC yield of 21.5% under the optimal reaction conditions. Moreover, benefiting from the larger micropore size, MOF-808-4 outperformed our previously reported UiO-66-24 (12-connected), which had even more acidic-basic sites and larger surface area than MOF-808-4, mainly because the larger micropore size of MOF-808-4 provided higher accessibility for the reactant to the active sites located in the micropores. Furthermore, a possible reaction mechanism over MOF-808-4 was proposed based on the in situ FT-IR results. The effects of different reaction parameters on DMC formation and the reusability of MOF-808-X were also studied.     

Mild and highly efficient method for the synthesis of 2-arylbenzimidazoles and 2-arylbenzothiazoles

A new, convenient method for the syntheses of 2-substituted benzimidazole and benzothizole is described. Short reaction times, large-scale synthesis, easy and quick isolation of the products, excellent chemoselectivity, and excellent yields are the main advantages of this procedure.     

Toward highly active electrochemical CO2 reduction to C2H4 by copper hydroxyphosphate

Journal of Solid State Electrochemistry - Electrocatalytic carbon dioxide reduction reaction (CO2RR) is a promising method to deal with the greenhouse effect and the energy crisis. In a...     

Single-atomic Fe anchored on hierarchically porous carbon frame for efficient oxygen reduction performance

Exploring platinum group metal-free electrocatalysts with superior catalytic performance and favorable durability for oxygen reduction reaction is a remaining bottleneck in process of developing sustainable techniques in energy storage and conversion. Herein, a hierarchical porous single atomic Fe electrocatalyst(Fe/Z8-E-C) is rationally designed and synthesized via acid etching, calcination, adsorption of Fe precursor and recalcination processes. This unique electrocatalyst Fe/Z8-E-C shows exce...     

Preparation of trimetallic electrocatalysts by one-step co-electrodeposition and efficient CO2 reduction to ethylene

Use of multi-metallic catalysts to enhance reactions is an interesting research area, which has attracted much attention. In this work, we carried out the first work to prepare trimetallic electrocatalysts by a one-step co-electrodeposition process. A series of Cu–X–Y (X and Y denote different metals) catalysts were fabricated using this method. It was found that Cu₁₀La₁Cs₁ (the content ratio of Cu²⁺, La³⁺, and Cs⁺ in the electrolyte is 10 : 1 : 1 in the deposition process), which had an elemental composition of Cu₁₀La_0.16Cs_0.14 in the catalyst, formed a composite structure on three dimensional (3D) carbon paper (CP), which showed outstanding performance for CO₂ electroreduction reaction (CO₂RR) to produce ethylene (C₂H₄). The faradaic efficiency (FE) of C₂H₄ could reach 56.9% with a current density of 37.4 mA cm⁻² in an H-type cell, and the partial current density of C₂H₄ was among the highest ones up to date, including those over the catalysts consisting of Cu and noble metals. Moreover, the FE of C₂₊ products (C₂H₄, ethanol, and propanol) over the Cu₁₀La₁Cs₁ catalyst in a flow cell reached 70.5% with a high current density of 486 mA cm⁻². Experimental and theoretical studies suggested that the doping of La and Cs into Cu could efficiently enhance the reaction efficiency via a combination of different effects, such as defects, change of electronic structure, and enhanced charge transfer rate. This work provides a simple method to prepare multi-metallic catalysts and demonstrates a successful example for highly efficient CO₂RR using non-noble metals.

Trimetallic Cu₁₀La₁Cs₁ catalysts prepared via a one-step co-electrodeposition strategy can act as a robust electrocatalyst for CO₂RR to C₂H₄.