Solar-Driven Continuous CO2 Reduction to CO and CH4 using Heterogeneous Photothermal Catalysts: Recent Progress and Remaining Challenges.

The urgent need to reduce the carbon dioxide level in the atmosphere and keep the effects of climate change manageable has brought the concept of carbon capture and utilization to the forefront of scientific research. Amongst the promising pathways for this conversion, sunlight-powered photothermal processes, synergistically using both thermal and non-thermal effects of light, have gained significant attention. Research in this field focuses both on the development of catalysts and continuous-flow photoreactors, which offer significant advantages over batch reactors, particularly for scale-up. Here, we focus on sunlight-driven photothermal conversion of CO2 to chemical feedstock CO and CH4 as synthetic fuel. This review provides an overview of the recent progress in the development of photothermal catalysts and continuous-flow photoreactors and outlines the remaining challenges in these areas. Furthermore, it provides insight in additional components required to complete photothermal reaction systems for continuous production (e. g., solar concentrators, sensors and artificial light sources). In addition, our review emphasizes the necessity of integrated collaboration between different research areas, like chemistry, material science, chemical engineering, and optics, to establish optimized systems and reach the full potential of this technology.

A combined continuous microflow photochemistry and asymmetric organocatalysis approach for the enantioselective synthesis of tetrahydroquinolines.

A continuous-flow asymmetric organocatalytic photocyclization-transfer hydrogenation cascade reaction has been developed. The new protocol allows the synthesis of tetrahydroquinolines from readily available 2-aminochalcones using a combination of photochemistry and asymmetric Brønsted acid catalysis. The photocylization and subsequent reduction was performed with catalytic amount of chiral BINOL derived phosphoric acid diester and Hantzsch dihydropyridine as hydrogen source providing the desired products in good yields and with excellent enantioselectivities.

Non-covalent binding tags for batch and flow biocatalysis.

Enzyme immobilization offers considerable advantage for biocatalysis in batch and continuous flow reactions. However, many currently available immobilization methods require that the surface of the carrier is chemically modified to allow site specific interactions with their cognate enzymes, which requires specific processing steps and incurs associated costs. Two carriers (cellulose and silica) were investigated here, initially using fluorescent proteins as models to study binding, followed by assessment of industrially relevant enzyme performance (transaminases and an imine reductase/glucose oxidoreductase fusion). Two previously described binding tags, the 17 amino acid long silica-binding peptide from the Bacillus cereus CotB protein and the cellulose binding domain from the Clostridium thermocellum, were fused to a range of proteins without impairing their heterologous expression. When fused to a fluorescent protein both tags conferred high avidity specific binding with their respective carriers (low nanomolar Kd values). The CotB peptide (CotB1p) induced protein aggregation in the transaminase and imine reductase/glucose oxidoreductase fusions when incubated with the silica carrier. The Clostridium thermocellum cellulose binding domain (CBDclos) allowed immobilization of all the proteins tested, but immobilization led to loss of enzymatic activity in the transaminases (< 2-fold) and imine reductase/glucose oxidoreductase fusion (> 80%). A transaminase-CBDclos fusion was then successfully used to demonstrate the application of the binding tag in repetitive batch and a continuous-flow reactor.

Deacidification of high-acid rice bran oil by the tandem continuous-flow enzymatic reactors.

Rice bran oil (RBO) contains a variety of nutrients, but the high acid values largely hinder its processing into edible oil. Thus, the tandem continuous-flow reactors are proposed and developed for the enzymatic deacidification of RBO and simultaneous production of functional oils. The results indicate that the Candida antarctica lipase B (CALB) immobilized on the hydrophobic ordered mesoporous silicon (OMS-C18) increased 6.6 times of the catalytic activity and improved at least 20 ℃ of temperature tolerance compared to the commercial Novozym 435. The tandem continuous-flow enzymatic reactors removed 91.4% of free fatty acid and increased 9 and 12 times of phytosterol ester and diacylglycerol in RBO, respectively. Moreover, the retention rate of γ-oryzanol was at least 40% higher than that obtained by traditional alkali refining. This study provides an effective and sustainable method to continuously convert the low-value RBO into value-added products, which brings huge potential to cleaner industrial production.

Microalgae-bacterial biomass outperforms PN-anammox biomass for oxygen saving in continuous-flow granular reactors facing extremely low-strength freshwater aquaculture streams.

The dissolved oxygen (DO) concentration in water streams is one of the most important and critical quality parameters in aquaculture farms. The main objective of this study was to evaluate the potential of two Continuous Flow Granular Reactors, one based on Partial Nitrification-Anammox biomass (Aquammox CFGR) and the other on Microalgae-Bacteria biomass (AquaMab CFGR), for improving dissolved oxygen availability in the recirculation aquaculture systems (RAS). Both reactors treated the extremely low-strength effluents from a freshwater trout farm (1.39 mg NH4+-N/L and 7.7 mg TOC/L). The Aquammox CFGR, removed up to 68% and 100% of ammonium and nitrite, respectively, but the DO concentration in the effluent was below 1 mg O2/L while the anammox activity was not maintained. In the AquaMab CFGR, bioaugmentation of aerobic granules with microalgae was attained, producing an effluent with DO concentrations up to 9 mg O2/L and removed up to 77% and 80% of ammonium and nitrite, respectively, which is expected to reduce the aeration costs in fish farms.

Comparison and Optimization of Continuous Flow Reactors for Aerobic Granule Sludge Cultivation from the Perspective of Hydrodynamic Behavior.

Improving treatment efficiency and reducing investment and operating costs make aerobic granular sludge technology (AGS) a promising technology for treating aquaculture wastewater. The development of continuous flow reactors (CFRs) has become a new direction in the research of AGS. This study clarifies the granulation effect, hydrodynamic behavior and particle separation of three different CFRs (R1 to R3). The established CFD model was able to explain the hydrodynamic behavior in all three CFRs; in particular, R3 performed the best from the perspective of hydrodynamic behavior due to its abundant turbulence. In addition, the optimal baffle distance and baffle angle of R3 were simulated to be 40 mm and 60°, respectively, due to them providing the best turbulent flow and particle separation effect. However, an overlarge baffle angle could weaken the turbulent pattern in the reactor. The retention time distribution further confirmed the reasonability of these optimal parameters with the highest effective volume ratio of 0.82. In short, this study gives an instruction for exploring the rapid formation mechanism of AGS in a CFR to promote its engineering application.

Research on rapid cultivation of aerobic granular sludge (AGS) with different feast-famine strategies in continuous flow reactor and achieving high-level denitrification via utilization of soluble microbial product (SMP).

The mixture of partial AGS and flocculent sludge in continuous flow reactors were operated with periodic famine (PF) strategy and continuous feast (CF) strategy to reveal the impact of the feast-famine strategies on cultivation of AGS and the dynamics of microbial communities. The experimental results showed that the mature AGS were cultivated with PF and CF strategy on the 31st and the 71st days respectively, which was the result of good extracellular polymeric substance (EPS) secretion with PF strategy. It could accelerate the formation of microbial aggregates due to the conditions of periodic famine. High-level denitrification with PF strategy via utilization of SMP was examined by EEM-PARAFAC on cycle test. The high-throughput pyrosequencing showed that the dominant bacteria with PF strategy involved functional bacteria of nutrient removal and EPS secreting bacteria, while the dominant bacteria were fast-growing heterotrophic organisms with CF strategy.

Easy-to-perform and cost-effective fabrication of continuous-flow reactors and their application for nanomaterials synthesis.

The translation of continuous-flow microreactor technology to the industrial environment has been limited by cost and complexity of the fabrication procedures and the requirement for specialised infrastructure. In the present study, we have developed a significantly more cost-effective and easy-to-perform fabrication method for the generation of optically transparent, continuous-flow reactors. The method combines 3D printing of master moulds with sealing of the PDMS channels' replica using a pressure-sensitive adhesive tape. Morphological characterisation of the 3D printed moulds was performed and reactors were fabricated with an approximately square-shaped cross-section of 1 mm2. Notably, they were tested for operation over a wide range of volumetric flow rates, up to 20 ml/min. Moreover, the fabrication time (i.e., from design to the finished product) was <1 day, at an average material cost of ∼£5. The flow reactors have been applied to the production of both inorganic nanoparticles (silver nanospheres) and organic vesicular systems (liposomes), and their performance compared with reactors produced using more laborious fabrication methods. Numerical simulations were performed to characterise the transport of fluids and chemical species within the devices. The developed fabrication method is suitable for scaled-up fabrication of continuous-flow reactors, with potential for application in biotechnology and nanomedicine.