Commodity Chemicals Research Articles

Markerless deletion of the putative type I and III restriction-modification systems in the cellulolytic bacterium Clostridium cellulovorans using a codBA-based counterselection technique

Cellulose from lignocellulosic biomass (LB) is of increasing interest for the production of commodity chemicals. However, its use as substrate for fermentations is a challenge due to its structural complexity. In this context, the highly cellulolytic Clostridium cellulovorans has been considered an interesting microorganism for the breakdown of LB. C. cellulovorans does not naturally produce solvents in useful concentrations, but this could be achieved by metabolic engineering. Unfortunately, this is hampered by the lack of tools for genetic engineering. We describe a genetic system that allows strain engineering by the allelic-coupled exchange method. First, the Gram-positive origin of pUB110 was identified as a suitable clostridial 'pseudo-suicide' origin of replication for the construction of deletion vectors. Second, an efficient counterselection strategy based on a codBA cassette and the use of 5-fluorocytosine as the counterselective compound was employed. Third, since the prevention of DNA transfer by host restriction-modification (RM) systems is a critical barrier to genome engineering, deletion plasmids containing flanking regions for the putative type I (Clocel_1114) and III (Clocel_2651) RM systems were constructed and transferred into C. cellulovorans. The restriction-less strains C. cellulovorans ΔClocel_1114 and C. cellulovorans ΔClocel_2651 exhibit high conjugation efficiency and can be easily used for further metabolic engineering.

Electrothermal synthesis of commodity chemicals

Electrothermal synthesis of commodity chemicals

Engineering heterojunction noble metal (NM)@ZnO catalyst for improved CH4 photocatalytic oxidation

The photo-oxidation of methane into value-oxygenated products using H2O2 and H2O as an oxidant under atmospheric pressure represents a desired sustainable strategy for the production of commodity chemicals. However, controlling the products and maintaining high yields poses significant challenges. In this study, we propose an efficient strategy involving the design of noble metal (Au, Pd)/ZnO photocatalysts to enhance the productivity of oxygenates through CH4 photocatalytic oxidation. The prominent product, CH3OH, is achieved with a high yield of 1900 μmol/g. The unique combination and porous structures of Au/ZnO synergistically promote its conversion performance. Additionally, photoluminescence results provide direct evidence of the main intermediates involved in producing CH3OH and multi-carbon oxygenates. The findings of this research offer valuable insights into the fundamental oxidation mechanisms underlying photocatalytic CH4 conversion.

Recycling Valuable Phenol from Polycarbonate Plastic Waste Via Direct Depolymerization and Csp2-Csp3 Bond Cleavage Under Mild Conditions.

Upcycling plastic waste into commodity chemicals is recognized as an environmentally benign solution and beneficial for the sustained growth of humanity. Nevertheless, transition metal-free catalysts and energy-efficient conditions pose significant challenges due to the robust mechanical properties of plastics. Here, a strategy for selective production of phenol by upcycling polycarbonate waste via direct depolymerization and Csp2-Csp3 bond cleavage in an aqueous medium under mild conditions is reported. The commercial zeolites efficiently catalyze the depolymerization, Csp2-Csp3 bond hydrolysis, and direct Csp2-Csp3 bond scission at Cα of PC. Among all evaluated zeolites, HY (Si/Al=15) showed excellent catalytic performance, attributed to the ~75 % yield of phenol and ~15 % of acetone. The approach also employs different municipal waste PC for upcycling. Studies reveal that HY (15) exhibits high catalytic efficiency and phenol yield due to its optimum acid sites and textual properties. A scale-up experiment demonstrated that 3.1 g of phenol was produced from 5.0 g of PC, and the mass balance was 90 %. A combination of control experiments, NMR analysis, and DFT studies proposed the reaction pathway. Our findings present a sustainable avenue for upcycling PC waste and offer a new way to produce phenol, contributing to the advancement of a circular economy.

Formate Salts: The Rediscovery of Their Radical Reaction under Light Irradiation Opens New Avenues in Organic Synthesis

AbstractFormates are abundantly available and inexpensive commodity chemical, widely used in laboratory and industrial organic synthesis. Formates are promising hydrogen carrier and green C1 source, and have also been a subject of research as SET reductants in recent years. Compared to the toxic and flammable gas carbon monoxide, which also serves as a C1 source, formates are easier to handle, store, and transport, and are more environmentally friendly. Therefore, in recent studies of radical reactions, formate is not only as an ideal source of green carbonyl, which is of great significance to synthesize carboxyl compounds with various structures, but also as a SET reductant for editing organic molecules either in scientific research or industrial production. The activation and conversion of formate, as a source of C1 or a SET reductant, is a very challenging and hot research field in organic synthesis.

Unlocking the Chemical and Structural Complexity of Aluminum Hydroxy Acetates: from Commodity Chemicals to Porous Materials.

Aluminum acetates have been in use for more than a century, but despite their widespread commercial applications, essential scientific knowledge of their synthesis-structure-property relationships is lacking. High-throughput screening, followed by fine tuning and extensive optimization of reaction conditions using Al3+, OH- and CH3COO- ions, has unraveled their complex synthetic chemistry, yielding for the first time the four phase pure products Al(OH)(O2CCH3) ⋅ x H2O (x = 0, 2) (1A and CAU-65, 1B), Al3O(HO2CCH3)(O2CCH3)7 (2), and the porous aluminum salt [Al24(OH)56(CH3COO)12](OH)4 (CAU-55-OH, 3). Structure determination by electron and X-ray diffraction was carried out and the data suggested porosity for 1B and 3, which was confirmed by physisorption experiments. Even the scale-up to the 10 L scale was accomplished for 1A, 1B and 3 with yields of up to 1.1 kg (99%). This study of a seemingly simple chemical system provides important information on both fundamental inorganic chemistry and porous materials.

Non-Noble Metal Anchored 2D Covalent Organic Framework for Ambient CO2 Fixation to High-Value Compounds.

The catalytic functionalization of CO2 into high-value compounds comprises a promising approach to mitigate its atmospheric content and sustainable generation of fine chemicals. Herein, we report application of a crystalline, nano-porous 2D COF (ET-BP-COF) for utilization of CO2. The ET-BP-COF features a unique 2D kagome (kgm) topology composed of hexagonal and triangular 1D channels decorated with bipyridine sites, which were exploited for covalent anchoring of eco-friendly Cu(I) by post-synthetic method. The Cu(I) engrafted COF was applied as a recyclable catalyst for coupling CO2 with alkynes to generate two high-value compounds, α-alkylidene cyclic carbonates (α-ACCs) and 2-oxazolidinones. Notably, Cu(I)@ET-BP-COF demonstrated excellent catalytic performance for transforming propargylic amine and CO2 to 2-oxazolidinone, an essential building block for antibiotics. Besides, an efficient transformation of propargylic alcohols to generate α-ACCs, valuable commodity chemicals, has been achieved by utilizing carbon dioxide. Further, detailed theoretical simulations disclosed the insight mechanistic path of Cu(I) catalyzed coupling of CO2 with alkynes to produce 2-oxazolidinones and α-ACCs. Significantly, Cu(I)@COF was reusable for multiple cycles without losing framework rigidity and catalytic performance. This study showcases the potential application of ET-BP-COF for stable anchoring of eco-friendly metals as catalytic sites for effective utilization of CO2 to produce two high-value products.

Pioneering precision in markerless strain development for Synechococcus sp. PCC 7002

Marine cyanobacteria such as Picosynechococcus sp. (formerly called Synechococcus sp.) PCC 7002 are promising chassis for photosynthetic production of commodity chemicals with low environmental burdens. Genetic engineering of cyanobacteria conventionally employs antibiotic resistance markers. However, limited availability of antibiotic-resistant markers is a problem for highly multigenic strain engineering. Although several markerless genetic manipulation methods have been developed for PCC 7002, they often lack versatility due to the requirement of gene disruption in the host strain. To achieve markerless transformation in Synechococcus sp. with no requirements for the host strain, this study developed a method in which temporarily introduces a mutated phenylalanyl-tRNA synthetase gene (pheS) into the genome for counter selection. Amino acid substitutions in the PheS that cause high susceptibility of PCC 7002 to the phenylalanine analog p-chlorophenylalanine were examined, and the combination of T261A and A303G was determined as the most suitable mutation. The mutated PheS-based selection was utilized for the markerless knockout of the nblA gene in PCC 7002. In addition, the genetic construct containing the lldD and lldP genes from Escherichia coli was introduced into the ldhA gene site using the counter selection strategy, resulting in a markerless recombinant strain. The repeatability of this method was demonstrated by the double markerless knockin recombinant strain, suggesting it will be a powerful tool for multigenic strain engineering of cyanobacteria.

Renaissance of Chlorine Evolution Reaction: Emerging Theory and Catalytic Materials

Chlorine (Cl2) is one of the most important commodity chemicals that has found widespread utility in chemical industry. Most Cl2 is currently produced via the chlorine evolution reaction (CER) at the anode of chlor–alkali electrolyzers, for which precious group‐metal‐based mixed metal oxides (MMOs) have been used for more than half a century. However, MMOs suffer from the use of platinum‐group metals, which are costly and scarce, and the selectivity issue arises from the parasitic oxygen evolution reaction. Over the last decade, the field of CER catalysis has seen dramatic advances in both the theory and discovery of new catalysts. Theoretical approaches have enabled a fundamental understanding of CER mechanisms and provided catalyst design principles. The exploration of new materials has led to the discovery of CER catalysts other than MMOs, including non‐PGM‐based oxides, atomically dispersed single‐site catalysts, and organic molecules, with some of which following novel reaction pathways. This minireview provides an overview of the recent advances in CER electrocatalyst research and suggests future directions for this revitalized field.

Renaissance of Chlorine Evolution Reaction: Emerging Theory and Catalytic Materials.

Chlorine (Cl2) is one of the most important commodity chemicals that has found widespread utility in chemical industry. Most Cl2 is currently produced via the chlorine evolution reaction (CER) at the anode of chlor-alkali electrolyzers, for which precious group-metal-based mixed metal oxides (MMOs) have been used for more than half a century. However, MMOs suffer from the use of platinum-group metals, which are costly and scarce, and the selectivity issue arises from the parasitic oxygen evolution reaction. Over the last decade, the field of CER catalysis has seen dramatic advances in both the theory and discovery of new catalysts. Theoretical approaches have enabled a fundamental understanding of CER mechanisms and provided catalyst design principles. The exploration of new materials has led to the discovery of CER catalysts other than MMOs, including non-PGM-based oxides, atomically dispersed single-site catalysts, and organic molecules, with some of which following novel reaction pathways. This minireview provides an overview of the recent advances in CER electrocatalyst research and suggests future directions for this revitalized field.

Microkinetic Model to Rationalize the Lifetime of Electrocatalysis: Trade-off between Activity and Stability.

Electrocatalysts which can operate for several years are required to produce hydrogen and commodity chemicals in an environmentally friendly manner. However, designing materials with long operational lifetimes is challenging, due to the lack of a conceptual framework to predict catalytic lifetimes quantitatively. Here, we report a microkinetic equation which quantifies the lifetime of an electrocatalyst undergoing dissolution. This equation was obtained by taking advantage of the fact that catalysis is much faster than deactivation, which allows the ordinary differential equations to be solved via the quasi steady-state approximation. All chemical reactions were modeled as irreversible, first-order elementary reactions. Under this assumption, the catalytic rate correlates linearly with the deactivation rate, leading to a trade-off relationship between activity and stability. Our model was supported by the correlation between theoretical and experimental lifetimes (r2 = 0.86) of a manganese oxide electrocatalyst during the oxygen evolution reaction.

Structure-Directed Quaternary Ammonium Hydroxide Resins: High-Performance Heterogeneous Base Catalysts for Continuous-Flow Carbon-Carbon Bond-Forming Reactions.

Quaternary ammonium hydroxide resins are widely recognized for their effectiveness as immobilized bases and are frequently utilized as commodity chemicals for anion-exchange applications. However, despite their accessibility, chemically controlling their properties has proven challenging, hindering research and development efforts toward their use as solid base catalysts. This study investigates the synthetic factors that are crucial for achieving high functional performance in polystyrene resins. Using commercially available resin as a benchmark and the continuous-flow Henry reaction as a model system, we explore and evaluate newly synthesized resin catalysts to maximize their basic catalytic activity.

Building Catalytic Reactions One Electron at a Time.

ConspectusClassical education in organic chemistry and catalysis, not the least my own, has centered on two-electron transformations, from nucleophilic attack to oxidative addition. The focus on two-electron chemistry is well-founded, as this brand of chemistry has enabled incredible feats of synthesis, from the development of life-saving pharmaceuticals to the production of ubiquitous commodity chemicals. With that said, this approach is in many ways complementary to the approach of nature, where enzymes frequently make use of single-electron "radical" steps to achieve challenging reactions with exceptional selectivity, including light detection and C-H hydroxylation. While the power of radical elementary steps is undeniable, the fundamental understanding of─and ability to apply─these in catalysis remains underdeveloped, constraining the palette with which chemists can make new reactions.Motivation to remedy this traditional underemphasis on radical catalysis has been intensified by the runaway success of outer-sphere photoredox catalysis, not only confirming the versatility of radicals in anthropogenic catalysis but also teaching the value of robust and well-understood catalytic cycles for reaction design. Indeed, I would argue the success of outer-sphere photoredox catalysis has been fueled by strong fundamental understanding of its underlying radical elementary steps, with consideration of single-electron transfer (SET) energetics allowing new reactions to be designed de novo with enviable confidence. However, outer-sphere photoredox catalysis is an outlier in this regard, with other mechanistic approaches remaining underexplored.Our research group is part of a growing movement to expand the vocabulary of synthetic radical catalysis beyond the traditional outer-sphere photoredox SET manifold, assembling new cycles comprised of hydrogen atom transfer (HAT), light-induced homolysis (LIH), and radical ligand transfer (RLT) steps in new combinations to achieve challenging transformations. These efforts have been made possible by the ever-growing understanding of these radical elementary steps and discovery of catalyst systems with significant mechanistic flexibility, most recently iron/thiol (Fe/S) cocatalysis.In this Account, I will focus on our efforts applying HAT and LIH steps in Fe/S cocatalysis, sharing broad guidelines we have found helpful for using these steps and demonstrating how they can be combined to make new reactions using three case studies: radical hydrogenation (HAT + HAT), decarboxylative protonation (LIH + HAT), and alkene hydrofluoroalkylation (LIH + HAT, with an intervening radical alkene addition). These efforts have highlighted the importance of several key parameters, including bond dissociation energy (BDE) and radical polarity, and I hope our findings similarly provide a valuable framework to others designing new radical catalytic reactions.

Process Development and Techno-Economic Analysis for Combined and Separated CO2 Capture-Electrochemical Utilization

Combining CO2 capture and utilization into a single unit operation offers a feasible solution for converting a sustainable feedstock into marketable commodity chemicals, while reducing energy requirements from separated processes. In this research, we developed a process model and performed a techno-economic analysis (TEA) for point-source CO2 capture and electrochemical-based utilization in light olefins production under both separated and integrated scenarios. CO2 containing flue gas from a 500 MW power plant was utilized as a feed while CO2 utilization involved electrochemical reduction reactions to produce light olefins directly from CO2. A meticulous analysis was conducted, probing into the multifaceted impacts of various operating parameters, material properties, and downstream treatment units. Factors such as pressure, temperature, H2O/CO2 molar ratio, catalyst and adsorbent activities, deactivation rate, and heat integration were optimized to achieve 95 % CO2 recovery and > 90 % conversion, and > 85 % ethylene yield. Through a comprehensive TEA, our findings unveiled that the combined process utilizing bifunctional adsorbent/catalyst materials (BFMs) incurs costs of approximately $284/ton CO2, whereas the separated process reported expenses of ∼$516/ton CO2. This study, pivotal in its contributions, evaluated economic feasibility of combined capture-conversion method based on BFMs for CO2 removal and subsequent utilization via a promising advanced process model for sustainable feedstocks conversion to commodity chemicals.

A growth-based screening strategy for engineering the catalytic activity of an oxygen-sensitive formate dehydrogenase.

Enzyme engineering is a powerful tool for improving or altering the properties of biocatalysts for industrial, research, and therapeutic applications. Fast and accurate screening of variant libraries is often the bottleneck of enzyme engineering and may be overcome by growth-based screening strategies with simple processes to enable high throughput. The currently available growth-based screening strategies have been widely employed for enzymes but not yet for catalytically potent and oxygen-sensitive metalloenzymes. Here, we present a screening system that couples the activity of an oxygen-sensitive formate dehydrogenase to the growth of Escherichia coli. This system relies on the complementation of the E. coli formate hydrogenlyase (FHL) complex by Mo-dependent formate dehydrogenase H (EcFDH-H). Using an EcFDH-H-deficient strain, we demonstrate that growth inhibition by acidic glucose fermentation products can be alleviated by FHL complementation. This allows the identification of catalytically active EcFDH-H variants at a readily measurable cell density readout, reduced handling efforts, and a low risk of oxygen contamination. Furthermore, a good correlation between cell density and formate oxidation activity was established using EcFDH-H variants with variable catalytic activities. As proof of concept, the growth assay was employed to screen a library of 1,032 EcFDH-H variants and reduced the library size to 96 clones. During the subsequent colorimetric screening of these clones, the variant A12G exhibiting an 82.4% enhanced formate oxidation rate was identified. Since many metal-dependent formate dehydrogenases and hydrogenases form functional complexes resembling E. coli FHL, the demonstrated growth-based screening strategy may be adapted to components of such electron-transferring complexes.IMPORTANCEOxygen-sensitive metalloenzymes are highly potent catalysts that allow the reduction of chemically inert substrates such as CO2 and N2 at ambient pressure and temperature and have, therefore, been considered for the sustainable production of biofuels and commodity chemicals such as ammonia, formic acid, and glycine. A proven method to optimize natural enzymes for such applications is enzyme engineering using high-throughput variant library screening. However, most screening methods are incompatible with the oxygen sensitivity of these metalloenzymes and thereby limit their relevance for the development of biosynthetic production processes. A microtiter plate-based assay was developed for the screening of metal-dependent formate dehydrogenase that links the activity of the tested enzyme variant to the growth of the anaerobically grown host cell. The presented work extends the application range of growth-based screening to metalloenzymes and is thereby expected to advance their adoption to biosynthesis applications.

Transcriptomic characterization of recombinant Clostridium beijerinckii NCIMB 8052 expressing methylglyoxal synthase and glyoxal reductase from Clostridium pasteurianum ATCC 6013.

Biological production of commodity chemicals from abundant waste streams such as whey permeate represents an opportunity for decarbonizing chemical production. Whey permeate remains a vastly underutilized feedstock for bioproduction purposes. Thus, enhanced understanding of the cellular and metabolic repertoires of lactose-mediated production of chemicals such as butanol promises to identify new targets that can be fine tuned in recombinant and native microbial strains to engender stronger coupling of whey permeate-borne lactose to value-added chemicals. Our results highlight new genetic targets for future engineering of C. beijerinckii for improved butanol production on lactose and ultimately in whey permeate.

Improving the yield of levoglucosan platform chemical from the pyrolysis of date pits waste biomass through pre-treatments

Lignocellulosic biomass, as the primary carbon source, serves as the foundation for the entire biorefinery concept. In this regard, date pits constitute an important category of biomass waste in many parts of the world. Levoglucosan, also known as 1,6-anhydro-β-d-glucopyranose (LG), is a significant sugar derivative and a platform chemical produced as a primary product in the cellulose pyrolysis process. Aiming to further improve the yield of levoglucosan from pyrolysis of date pits, pre-treatment methods were carried out via washing crushed date pits with different concentrations of selected acids (sulfuric acid: 1 M/3 M, nitric acid:1 M/3 M), and with hot water. The chemical and elemental compositions of the five considered samples were thoroughly analyzed and characterized by a wide array of ultimate and proximate techniques such as Neutral Detergent Fiber (NDF %), ASH content and organic Matter (%), and Mineral Nutrients Profile (ppm). By utilizing Py-GC/MS system, the product distribution from pyrolysis of raw and treated date pits was obtained at a range of temperatures between 300 and 500 °C. Compared to the raw date pits, pyrolysis of treated date pits pre-treated by 1 M H2SO4 acid exhibited a dramatic increase in the concentration of levoglucosan due to the profound removal of the various categories of minerals in date pits and an increase in the NDF %. A positive correlation prevails between the removal efficiency of alkali/alkaline earth metals (AAEMs) and the yield of LG. The former catalyzes ring-opening reaction that results in the destruction of sugar derivatives. On the other hand, pre-treatment with water also increases the yield of LG compared to raw date pits, but to a lesser extent. Outcomes demonstrated herein convey a practical method to enhance the production of commodity chemicals from waste biomass.

Toward the Use of Methyl-Coenzyme M Reductase for Methane Bioconversion Applications.

ConspectusAs the main component of natural gas and renewable biogas, methane is an abundant, affordable fuel. Thus, there is interest in converting these methane reserves into liquid fuels and commodity chemicals, which would contribute toward mitigating climate change, as well as provide potentially sustainable routes to chemical production. Unfortunately, specific activation of methane for conversion into other molecules is a difficult process due to the unreactive nature of methane C-H bonds. The use of methane activating enzymes, such as methyl-coenzyme M reductase (MCR), may offer a solution. MCR catalyzes the methane-forming step of methanogenesis in methanogenic archaea (methanogens), as well as the initial methane oxidation step during the anaerobic oxidation of methane (AOM) in anaerobic methanotrophic archaea (ANME). In this Account, we highlight our contributions toward understanding MCR catalysis and structure, focusing on features that may tune the catalytic activity. Additionally, we discuss some key considerations for biomanufacturing approaches to MCR-based production of useful compounds.MCR is a complex enzyme consisting of a dimer of heterotrimers with several post-translational modifications, as well as the nickel-hydrocorphin prosthetic group, known as coenzyme F430. Since MCR is difficult to study in vitro, little information is available regarding which MCRs have ideal catalytic properties. To investigate the role of the MCR active site electronic environment in promoting methane synthesis, we performed electric field calculations based on molecular dynamics simulations with a MCR from Methanosarcina acetivorans and an ANME-1 MCR. Interestingly, the ANME-1 MCR active site better optimizes the electric field with methane formation substrates, indicating that it may have enhanced catalytic efficiency. Our lab has also worked toward understanding the structures and functions of modified F430 coenzymes, some of which we have discovered in methanogens. We found that methanogens produce modified F430s under specific growth conditions, and we hypothesize that these modifications serve to fine-tune the activity of MCR.Due to the complexity of MCR, a methanogen host is likely the best near-term option for biomanufacturing platforms using methane as a C1 feedstock. M. acetivorans has well-established genetic tools and has already been used in pilot methane oxidation studies. To make methane oxidation energetically favorable, extracellular electron acceptors are employed. This electron transfer can be facilitated by carbon-based materials. Interestingly, our analyses of AOM enrichment cultures and pure methanogen cultures revealed the biogenic production of an amorphous carbon material with similar characteristics to activated carbon, thus highlighting the potential use of such materials as conductive elements to enhance extracellular electron transfer.In summary, the possibilities for sustainable MCR-based methane conversions are exciting, but there are still some challenges to tackle toward understanding and utilizing this complex enzyme in efficient methane oxidation biomanufacturing processes. Additionally, further work is necessary to optimize bioengineered MCR-containing host organisms to produce large quantities of desired chemicals.

Isolated Pt Atoms Stabilized by Ga2O3 Clusters Confined in ZSM-5 for Nonoxidative Activation of Ethane.

Selective activation of light alkanes is an essential reaction in the petrochemical industry for producing commodity chemicals, such as light olefins and aromatics. Because of the much higher intrinsic activities of noble metals in comparison to non-noble metals, it is desirable to employ solid catalysts with low noble metal loadings to reduce the cost of catalysts. Herein, we report the introduction of a tiny amount of Pt (at levels of hundreds of ppm) as a promoter of the Ga2O3 clusters encapsulated in ZSM-5 zeolite, which leads to ∼20-fold improvement in the activity for ethane dehydrogenation reaction. A combination of experimental and theoretical studies shows that the isolated Pt atoms stabilized by small Ga2O3 clusters are the active sites for activating the inert C-H bonds in ethane. The synergy of atomically dispersed Pt and Ga2O3 clusters confined in the 10MR channels of ZSM-5 can serve as a bifunctional catalyst for the direct ethane-benzene coupling reaction for the production of ethylbenzene, surpassing the performances of the counterpart catalysts made with PtGa nanoclusters and nanoparticles.

Photocatalytic CO2 Reduction by Near‐Infrared‐Light (1200 nm) Irradiation and a Ruthenium‐Intercalated NiAl‐Layered Double Hydroxide

AbstractNear‐infrared light‐driven photocatalytic CO2 reduction (NIR‐CO2PR) holds tremendous promise for the production of valuable commodity chemicals and fuels. However, designing photocatalysts capable of reducing CO2 with low energy NIR photons remains challenging. Herein, a novel NIR‐driven photocatalyst comprising an anionic Ru complex intercalated between NiAl‐layered double hydroxide nanosheets (NiAl‐Ru‐LDH) is shown to deliver efficient CO2 photoreduction (0.887 μmol h−1) with CO selectivity of 84.81 % under 1200 nm illumination and excellent stability over 50 testing cycles. This remarkable performance results from the intercalated Ru complex lowering the LDH band gap (0.98 eV) via a compression‐related charge redistribution phenomenon. Furthermore, transient absorption spectroscopy data verified light‐induced electron transfer from the Ru complex towards the LDH sheets, increasing the availability of electrons to drive CO2PR. The presence of hydroxyl defects in the LDH sheets promotes the adsorption of CO2 molecules and lowers the energy barriers for NIR‐CO2PR to CO. To our knowledge, this is one of the first reports of NIR‐CO2PR at wavelengths up to 1200 nm in LDH‐based photocatalyst systems.