Recent Trends,Benchmarking, and Challenges of Electrochemical Reduction of CO2 by Molecular Catalysts

CO₂ reduction using molecular catalysts is a key area of study for achieving electrical‐to‐chemical energy storage and feedstock chemical synthesis. Compared to classical metallic solid‐state catalysts, these molecular catalysts often result in high performance and selectivity, even under unfavorable aqueous environments. This review considers the recent state‐of‐the‐art molecular catalysts for CO₂ electroreduction and explains the observed performance, therefore guiding the design principles for the next generation of molecules and material/molecule hybrid electrodes. The most recent advances related to these issues are discussed.     

Nanoporous Au Thin Films on Si Photoelectrodes for Selective and Efficient Photoelectrochemical CO2 Reduction

An Si photoelectrode with a nanoporous Au thin film for highly selective and efficient photoelectrochemical (PEC) CO₂ reduction reaction (CO₂RR) is presented. The nanoporous Au thin film is formed by electrochemical reduction of an anodized Au thin film. The electrochemical treatments of the Au thin film critically improve CO₂ reduction catalytic activity of Au catalysts and exhibit CO Faradaic efficiency of 96% at 480 mV of overpotential. To apply the electrochemical pretreatment of Au films for PEC CO₂RR, a new Si photoelectrode design with mesh‐type co‐catalysts independently wired at the front and the back of the photoelectrode is demonstrated. Due to the superior CO₂RR activity of the nanoporous Au mesh and high photovoltage from Si, the Si photoelectrode with the nanoporous Au thin film mesh shows conversion of CO₂ to CO with 91% Faradaic efficiency at positive potential than the CO₂/CO equilibrium potential.     

CO2对微拟球藻(Nannochloropsis sp.)利用有机碳和光合作用的影响

CO2浓度提高时,微拟球藻吸收醋酸钠的速率增加2倍。混养生长的藻细胞最大光合作用速率、光合作用效率、无机碳半饱和常数和无机碳饱和的光合作用速率均显著低于光自养条件下生长的。     

Electrochemical CO2 Reduction Using Electrons Generated from Photoelectrocatalytic Phenol Oxidation

Electrochemical CO₂ reduction (ECCO₂R) requires electrons, for example, from oxygen evolution reaction (OER). However, such a multiple‐electron‐involved reaction is complicated and kinetically slow, leading to high overpotential. Herein, OER is replaced with photoelectrocatalytic phenol oxidation reaction (PECPOR) that provides electrons for ECCO₂R. In an integrated cell, ECCO₂R is conducted on the cathode of Cu nanowires and PECPOR is performed on the anode of SnO₂ and Sb coated TiO₂ nanotubes. Significant improvement of ECCO₂R into CO and hydrocarbons is realized when PECPOR is conducted at a high current density. The use of this integrated system results in the reduction of the specific energy consumption by a factor of 51.33%, compared with the utilization of two half‐cells for individual ECCO₂R and PECPOR. This study thus proposes a novel strategy to couple ECCO₂R with PECPOR and eventually to tackle the problems of environmental pollution and energy crisis.     

CO2倍增条件下长白赤松幼苗土壤CO2廓线的动态

采用固定在土壤中的气井系统,监测土壤剖面的CO2动态及其与长白赤松 (Pinus sylvestris var. sylvestriformis (Takenouchi) Cheng et C. D. Chu) 幼苗根系发展之间的关系.实验研究共设4种CO2处理,分别是环境CO2浓度,无苗;CO2为700 μmol/mol,无苗;环境CO2浓度,有苗;CO2为700 μmol/mol,有苗.通过对土壤剖面CO2气体的同步采集与分析表明:土壤CO2廓线与幼苗根系的生物活性密切相关.在土壤表面及壤土和沙土的边界层中,根系分布密集,根系的呼吸作用对那两个土层CO2贡献大;随着幼苗的季节生长,与环境CO2浓度比较,CO2倍增将导致土壤剖面上CO2浓度最大区域由表面向壤土和沙土边界层的转移.本文采用的气井系统提供了一种对土壤无破坏、经济、简单并且能够用于监测幼苗地下过程的廓线研究方法.     

Surface Functionalization and Defect Construction of SnO2 with Amine Group for Enhanced Visible-Light-Driven Photocatalytic CO2 Reduction

Photocatalytic CO₂ reduction to hydrocarbon fuels through solar energy provides a feasible channel for reducing CO₂ emission and resource depletion. Nevertheless, severe charge recombination and high energy barrier limit the CO₂ reduction efficiency. Herein, a surface amine-functionalized SnO₂ with oxygen vacancies (A-Vo-SnO₂) is fabricated to achieve visible-light-driven photocatalytic CO₂ reduction. Specifically, amino groups modified onto the surface of the catalyst can provide more active sites to promote the adsorption of CO₂. Meanwhile, the synchronously induced oxygen defect level reduces the band-gap energy and expands the light-absorption region from UV light to visible light. The oxygen vacancies can modulate the electronic structure and work as the separation centers of spatial charges, thus promoting the interfacial charge transfer efficiency and providing more catalytic sites, as evidenced by experimental observation and theoretical calculation. As expected, this A-Vo-SnO₂ exhibits a CH₄ evolution rate of 17.27 µmol g⁻¹ h⁻¹ without adding sacrificial agent and co-catalyst, much higher than 5.98 µmol g⁻¹ h⁻¹ of pure SnO₂. This work can provide significant inspiration for the design of defect engineering based on visible-light-driven photocatalysts towards photocatalytic CO₂ conversion.     

钙化藻类的钙化过程与大气中CO2浓度变化的关系

大气中CO2浓度升高后,CO2向海水的溶入增加,从而引起海水溶解无机碳各组分的浓度及其比例发生改变,导致海水酸化(pH下降)。此种环境的变化会影响钙化藻类的钙化过程。文章介绍钙化藻类的光合作用和钙化作用之间相互关系的研究进展。     

Tomographic Reconstruction and Analysis of a Silver CO2 Reduction Cathode

Tomographic reconstruction has been well established as a valuable tool in the analysis of polymer electrolyte fuel cell (PEMFC) electrodes. While forays have been made into applying it to polymer electrolyte water electrolyzer (PEMWE) electrodes, CO₂ electrolyzer electrodes are still new ground. Here a tomographic analysis of an electrochemical CO₂ reduction gas diffusion electrode by means of focused ion beam scanning electron microscope tomography is presented. The reconstruction shows a porosity of 68%. While most of the porosity is on the nanoscale, a broad tail of micropores is observed in the distribution. The spatial distribution of the pores is nonuniform. The large pores are concentrated in the center of the layer in the through‐plane direction. From the reconstruction, an effective diffusivity factor of 0.5 for the catalyst layer is calculated. The Knudsen number of 0.19 obtained from the later shows that the diffusion is mostly in the bulk regime. Flooding of the catalyst layer is likely to decrease the effective diffusivity factor substantially.     

Rational Design of Nanocatalysts with Nonmetal Species Modification for Electrochemical CO2 Reduction

Converting CO₂ to valuable carbonaceous fuels and chemicals via electrochemical CO₂ reduction by using renewable energy sources is considered to be a scalable strategy with substantial environmental and economic benefits. One of the challenges in this field is to develop nanocatalysts with superior electrocatalytic activity and selectivity for targeted products. Nonmetal species modification of nanocatalysts is of great significance for the construction of distinctive active sites to overcome the kinetic limitations of CO₂ reduction. These types of modification enable the efficient control of the selectivity and significantly decrease the reaction overpotential. Herein, a comprehensive review of the recent progress of nonmetal species modification of nanocatalysts for electrochemical CO₂ reduction is presented. After discussing some fundamental parameters and the basic principles of CO₂ reduction, including possible reaction pathways in light of theoretical modeling and experiments, the identification of active sites and elucidation of reaction mechanisms are emphasized for unraveling the role of nonmetal species modification, such as heteroatom incorporation, organic molecule decoration, electrolyte engineering, and single‐atom engineering. In the final section, future challenges and constructive perspectives are provided, facilitating the accelerated advancement of mechanism research and practical applications of green carbon cycling.     

高浓度CO2培养条件下极大螺旋藻光抑制研究

以极大螺旋藻作为实验材料,研究了不同CO2浓度培养对螺旋藻光抑制和恢复的影响,结果表明由光抑制导致的光合速率下降,高浓度CO2比低浓度CO2培养程度小,在高浓度CO2条件下培养的极大螺旋藻,虽然在强光下也表现出光抑制,但与低浓度CO2相比,光合速率下降得较慢。这种现象在强光与弱光培养均存在,但强光培养时更明显。光抑制后的恢复实验表明,不同CO2浓度培养的极大螺旋藻,光系统光化学活性(Fv/Fm)在弱光下恢复较好,高光强、高浓度CO2培养的藻,恢复速度稍快;而在黑暗中,几乎没有恢复;在弱光和含氯霉素的条件下Fv/Fm均下降。由此可见,高CO2浓度可减轻极大螺旋藻的光抑制,但对其光抑制后的恢复影响不大。       

LI-6262 CO2/H2O分析仪接气室法在草原群落蒸散量与CO2交换量测定中的应用

植物群落蒸散量和CO2交换量的测定方法多种多样.该文以水分、CO2动态的区域性整合为目标,开创了一种新的、同时测定群落蒸散量和CO2交换量的方法--LI-6262 CO2/H2O分析仪接气室法.借助这种方法测定了内蒙古锡林河流域典型草原区群落蒸散量和CO2交换量,取得了较好的结果.该方法将群落的重要生态过程:蒸散与光合、呼吸作用的测定联系起来,也因此得到一系列表征群落特性的有用指标;同时该方法具有精度高、简便易携带、适于野外操作等特点,经进一步改进后可广泛用于草原、沙地及湿地植物群落的气体通量测定.对于精确研究草原区各种植物群落类型的水分利用、光合和呼吸特性及草原区植被在全球气候变化中的地位和作用等有重要的实用价值.     

Reduction of transpiration and altered nutrient allocation contribute to nutrient decline of crops grown in elevated CO2 concentrations

Plants grown in elevated [CO₂] have lower protein and mineral concentrations compared with plants grown in ambient [CO₂]. Dilution by enhanced production of carbohydrates is a likely cause, but it cannot explain all of the reductions. Two proposed, but untested, hypotheses are that (1) reduced canopy transpiration reduces mass flow of nutrients to the roots thus reducing nutrient uptake and (2) changes in metabolite or enzyme concentrations caused by physiological changes alter requirements for minerals as protein cofactors or in other organic complexes, shifting allocation between tissues and possibly altering uptake. Here, we use the meta‐analysis of previous studies in crops to test these hypotheses. Nutrients acquired mostly by mass flow were decreased significantly more by elevated [CO₂] than nutrients acquired by diffusion to the roots through the soil, supporting the first hypothesis. Similarly, Mg showed large concentration declines in leaves and wheat stems, but smaller decreases in other tissues. Because chlorophyll requires a large fraction of total plant Mg, and chlorophyll concentration is reduced by growth in elevated [CO₂], this supports the second hypothesis. Understanding these mechanisms may guide efforts to improve nutrient content, and allow modeling of nutrient changes and health impacts under future climate change scenarios.     

Inhibitory effect of carbon dioxide on the fed-batch culture of Ralstonia eutropha: evaluation by CO2 pulse injection and autogenous CO2 methods

In order to see the effect of CO(2) inhibition resulting from the use of pure oxygen, we carried out a comparative fed-batch culture study of polyhydroxybutyric acid (PHB) production by Ralstonia eutropha using air and pure oxygen in 5-L, 30-L, and 300-L fermentors. The final PHB concentrations obtained with pure O(2) were 138.7 g/L in the 5-L fermentor and 131.3 g/L in the 30-L fermentor, which increased 2.9 and 6.2 times, respectively, as compared to those obtained with air. In the 300-L fermentor, the fed-batch culture with air yielded only 8.4 g/L PHB. However, the maximal CO(2) concentrations in the 5-L fermentor increased significantly from 4.1% (air) to 15.0% (pure O(2)), while it was only 1.6% in the 30-L fermentor with air, but reached 14.2% in the case of pure O(2). We used two different experimental methods for evaluating CO(2) inhibition: CO(2) pulse injection and autogenous CO(2) methods. A 10 or 22% (v/v) CO(2) pulse with a duration of 3 or 6 h was introduced in a pure-oxygen culture of R. eutropha to investigate how CO(2) affects the synthesis of biomass and PHB. CO(2) inhibited the cell growth and PHB synthesis significantly. The inhibitory effect became stronger with the increase of the CO(2) concentration and pulse duration. The new proposed autogenous CO(2) method makes it possible to place microbial cells under different CO(2) level environments by varying the gas flow rate. Introduction of O(2) gas at a low flow rate of 0.42 vvm resulted in an increase of CO(2) concentration to 30.2% in the exit gas. The final PHB of 97.2 g/L was obtained, which corresponded to 70% of the PHB production at 1.0 vvm O(2) flow rate. This new method measures the inhibitory effect of CO(2) produced autogenously by cells through the entire fermentation process and can avoid the overestimation of CO(2) inhibition without introducing artificial CO(2) into the fermentor.     

LI-6262CO2／H2O分析仪接气室法在草原群落蒸散量与CO2交换量测定中的应用

植物群落蒸散量和CO2交换量的测定方法多种多样。该文以水分、CO2动态的区域性整合为目标,开创了一种新的、同时测定群落蒸散量和CO2交换量的方法——LI—6262CO2／H2O分析仪接气窒法。借助这种方法测定了内蒙古锡林河流域典型草原区群落蒸散量和CO2交换量,取得了较好的结果。该方法将群落的重要生态过程2蒸散与光合、呼吸作用的测定联系起来,也因此得到一系列表征群落特性的有用指标;同时该方法具有精度高、简便易携带、适于野外操作等特点,经进一步改进后可广泛用于草原、沙地及湿地植物群落的气体通量测定。对于精确研究草原区各种植物群落类型的水分利用、光合和呼吸特性及草原区植被在全球气候变化中的地位和作用等有重要的实用价值。