Catalysts For CO2 Reduction Research Articles

Dramatic Improvement of Homogeneous Carbon Dioxide and Bicarbonate Electroreduction Using a Tetracationic Water-Soluble Cobalt Phthalocyanine.

Electrochemical conversion of carbon dioxide (CO2) offers the opportunity to transform a greenhouse gas into valuable starting materials, chemicals, or fuels. Since many CO2 capture strategies employ aqueous alkaline solutions, there is interest in catalyst systems that can act directly on such capture solutions. Herein, we demonstrate new catalyst designs where the electroactive molecules readily mediate the CO2-to-CO conversion in aqueous solutions between pH 4.5 and 10.5. Likewise, the production of CO directly from 2 M KHCO3 solutions (pH 8.2) is possible. The improved molecular architectures are based on cobalt(II) phthalocyanine and contain four cationic trimethylammonium groups that confer water solubility and contribute to the stabilization of activated intermediates via a concentrated positive charge density around the active core. Turnover frequencies larger than 103 s-1 are possible at catalyst concentrations of down to 250 nM in CO2-saturated solutions. The observed rates are substantially larger than the related cobalt phthalocyanine-containing catalysts. Density functional theory calculations support the idea that the excellent catalytic properties are attributed to the ability of the cationic groups to stabilize CO2-bound reduced intermediates in the catalytic cycle. The homogeneous, aqueous CO2 reduction that these molecules perform opens new frontiers for further development of the CoPc platform and sets a greatly improved baseline for CoPc-mediated CO2 upconversion. Ultimately, this discovery uncovers a strategy for the generation of platforms for practical CO2 reduction catalysts in alkaline solutions.

Pincer shaped N-Mesoionic Pyridylidene Amide (PYA) for palladium catalyzed CO2 reduction

Palladium complexes (4-6) bearing mesoionic N-donor pyridylidene amide ligands (PYAs) with different pendant groups of varying size and electronic properties were successfully synthesized from their respective pro-ligands (1-3). 4-6 were proved effective catalysts for CO2 reduction to synthesis gas. The first principle quantum studies of CO2 reduction provided better insight into the mechanism of these active catalysts. The highest selectivity of 71 % (Faradaic efficiency) and minimum overpotential of 0.390 V was observed for CO. Controlled potential electrolysis (CPE) and post-CPE cyclic voltammogram manifested that all catalysts were robust.

Exploring the Photophysics and Photocatalytic Activity of Heteroleptic Rh(III) Transition-Metal Complexes Using High-Throughput Experimentation.

High-throughput synthesis and screening (HTSS) methods were used to investigate the photophysical properties of 576 heteroleptic Rh(III) transition-metal complexes through measurement of the UV-visible absorption spectra, deaerated excited-state lifetime, and phosphorescent emission spectra. While 4d transition-metal photophysics are often highly influenced by deleterious metal-centered deactivation channels, the HTSS of structurally diverse cyclometalating and ancillary ligands attached to the metal center facilitated the discovery of photoactive complexes exhibiting long-lived charge-transfer phosphorescence (0.15-0.95 μs) spanning a substantial portion of the visible region (546-620 nm) at room temperature. Further photophysical and electrochemical investigations were then carried out on select complexes with favorable photophysics to understand the underlying features controlling these superior properties. Heteroleptic Ir(III) complexes with identical ligand morphology were also synthesized to compare these features to this family of well understood chromophores. A number of these Rh(III) complexes contained the requisite properties for photocatalytic activity and were consequently tested as photocatalysts (PCs) in a water reduction system using a Pd water reduction cocatalyst. Under certain conditions, the activity of the Rh(III) PC actually surpassed that of the Ir(III) PC, uncovering the potential of this often-overlooked class of transition metals as both efficient photoactive chromophores and PCs.

Carbon quantum dot-modified TiO2/SrTiO3 heterojunction for boosting photocatalytic CO2 reduction

An efficient carbon quantum dot (CQD)-modified TiO2/SrTiO3 heterojunction was constructed for photocatalytic CO2 reduction in this paper. Photogenerated electrons of SrTiO3 transferred to TiO2 via the transfer channel of CQDs for electron-hole recombination, while the photogenerated electrons migrated from TiO2 to CQDs to participate in the photocatalytic CO2 reduction reaction. Meanwhile, the up-conversion of CQDs enhanced the light harvesting ability of the catalyst and the CQDs enriched the active reaction sites. Due to the above advantages, the CO and CH4 produce rate over 0.1-CTS reached 54.9 and 35.9 μmol g−1 h−1, respectively, which was dramatically increased compared with pure TiO2 and pure SrTiO3. This work proposes a feasible strategy for integrating CQDs with TiO2 and SrTiO3 for the optimistic cooperative effect to obtain an effective catalyst for photocatalytic CO2 reduction.

Boosting visible-light-driven photocatalytic H2 production by optimizing surface hydrogen desorption of NiS/CdS–P photocatalyst

Metal chalcogenides are regarded as favorable H2-evolution cocatalysts; however, they often exhibit unfavorable H desorption characteristics due to the strong affinity of nascent H and highly electronegative S sites, which significantly inhibit H2 generation. To address this issue, a general approach to electron-enriched control of sulfur-active sites is developed for weakening the strong interaction of S–H bonds. This is achieved through the formation of a nanostructured model composed of NiS/CdS–P, in which the surface phosphorus (P) atoms are incorporated in CdS NRs to create an imbalanced charge distribution and a localized built-in electric field in the crystal structure of CdS. In this situation, the built-in electric field not only separates the photogenerated electron hole pairs, but it also accelerates the photogenerated electrons from the CdS–P conduction band to the NiS surface for rapid hydrogen reduction rather than hydrogen adsorption. Photocatalytic tests show that the resultant NiS/CdS–P photocatalyst displays a significant H2-generation rate of 44.39 mmol g−1 h−1 and an apparent quantum efficiency of 41% at 420 nm. Valance band XPS analysis shows that CdS–P has a higher electron density than CdS, leading to the production of electron-rich Sδ− active centers. This better photocatalytic hydrogen generation might be due to the synergistic impact of tailoring the intrinsic built-in electric field for the acceleration of photogenerated charges by P-doping and the fabrication of a NiS cocatalyst for hydrogen reduction rather than hydrogen adsorption. The concept of optimizing the electron densities of active sites by morphology tailoring, with an extra built-in electric field, gives a method for rationally constructing artificial photocatalysts for solar power conversion.

Selective scission of glucose molecule by a Pd-modulated Co-based catalyst for efficient CO2 reduction under mild conditions

Combining terrestrial biomass as the reductant with submarine-type hydrothermal environments for CO2 reduction represents a possible approach for novel energy production systems that sustainably circulate carbon. However, increasing the reductive power of biomass is the main limitation of this potential method. Herein, we demonstrate that Co-doped with small amounts of Pd enhances the reduction of CO2 by selectively producing an active intermediate from carbohydrates. This catalytic reaction utilized glucose as a reductant to achieve high formate production efficiency (458.6 g kg−1) with nearly 100% selectivity with 7.5 wt% Pd1Co20/γ–Al2O3 at a moderate temperature of 225 °C. The regulation of the electronic structure of the catalytic Co surface by the dopant Pd plays a key role in promoting the C–C bond cleavage of glucose and hydrogen transfer for CO2 reduction. The findings presented here indicate that biomass can serve as the hydrogen source for CO2 reduction and provide insight into the potential utilization of CO2 in sustainable industrial applications.

Organic Semiconductor-BiVO4 Tandem Devices for Solar-Driven H2O and CO2 Splitting.

Photoelectrochemical (PEC) devices offer a promising platform toward direct solar light harvesting and chemical storage through artificial photosynthesis. However, most prototypes employ wide bandgap semiconductors, moisture-sensitive inorganic light absorbers, or corrosive electrolytes. Here, the design and assembly of PEC devices based on an organic donor-acceptor bulk heterojunction (BHJ) using a carbon-based encapsulant are introduced, which demonstrate long-term H2 evolution and CO2 reduction in benign aqueous media. Accordingly, PCE10:EH-IDTBR photocathodes display long-term H2 production for 300 h in a near-neutral pH solution, whereas photocathodes with a molecular CO2 reduction catalyst attain a CO:H2 selectivity of 5.41±0.53 under 0.1 sun irradiation. Their early onset potential enables the construction of tandem PCE10:EH-IDTBR - BiVO4 artificial leaves, which couple unassisted syngas production with O2 evolution in a reactor completely powered by sunlight, sustaining a 1:1 ratio of CO to H2 over 96 h of operation.

Selective and stable CO2 electroreduction at high rates via control of local H2O/CO2 ratio

Controlling the concentrations of H2O and CO2 at the reaction interface is crucial for achieving efficient electrochemical CO2 reduction. However, precise control of these variables during catalysis remains challenging, and the underlying mechanisms are not fully understood. Herein, guided by a multi-physics model, we demonstrate that tuning the local H2O/CO2 concentrations is achievable by thin polymer coatings on the catalyst surface. Beyond the often-explored hydrophobicity, polymer properties of gas permeability and water-uptake ability are even more critical for this purpose. With these insights, we achieve CO2 reduction on copper with Faradaic efficiency exceeding 87% towards multi-carbon products at a high current density of −2 A cm−2. Encouraging cathodic energy efficiency (>50%) is also observed at this high current density due to the substantially reduced cathodic potential. Additionally, we demonstrate stable CO2 reduction for over 150 h at practically relevant current densities owning to the robust reaction interface. Moreover, this strategy has been extended to membrane electrode assemblies and other catalysts for CO2 reduction. Our findings underscore the significance of fine-tuning the local H2O/CO2 balance for future CO2 reduction applications.

Silicon photocathode functionalized with osmium complex catalyst for selective catalytic conversion of CO2 to methane

Solar-driven CO2 reduction to yield high-value chemicals presents an appealing avenue for combating climate change, yet achieving selective production of specific products remains a significant challenge. We showcase two osmium complexes, przpOs, and trzpOs, as CO2 reduction catalysts for selective CO2-to-methane conversion. Kinetically, the przpOs and trzpOs exhibit high CO2 reduction catalytic rate constants of 0.544 and 6.41 s−1, respectively. Under AM1.5 G irradiation, the optimal Si/TiO2/trzpOs have CH4 as the main product and >90% Faradaic efficiency, reaching −14.11 mA cm−2 photocurrent density at 0.0 VRHE. Density functional theory calculations reveal that the N atoms on the bipyrazole and triazole ligands effectively stabilize the CO2-adduct intermediates, which tend to be further hydrogenated to produce CH4, leading to their ultrahigh CO2-to-CH4 selectivity. These results are comparable to cutting-edge Si-based photocathodes for CO2 reduction, revealing a vast research potential in employing molecular catalysts for the photoelectrochemical conversion of CO2 to methane.

Interfacial engineering of Ag/C catalysts for practical electrochemical CO2 reduction to CO.

Electrochemical CO2 reduction to value-added chemicals by renewable energy sources is a promising way to implement the artificial carbon cycle. During the reaction, especially at high current densities for practical applications, the complex interaction between the key intermediates and the active sites would affect the selectivity, while the reconfiguration of electrocatalysts could restrict the stability. This paper describes the fabrication of Ag/C catalysts with a well-engineered interfacial structure, in which Ag nanoparticles are partially encapsulated by C supports. The obtained electrocatalyst exhibits CO Faradaic efficiencies (FEs) of over 90% at current densities even as high as 1.1 A/cm2. The strong interfacial interaction between Ag and C leads to highly localized electron density that promotes the rate-determining electron transfer step by enhancing the adsorption and the stabilization of the key *COO‒ intermediate. In addition, the partially encapsulated structure prevents the reconfiguration of Ag during the reaction. Stable performance for over 600 h at 500 mA/cm2 is achieved with CO FE maintaining over 95%, which is among the best stability with such a high selectivity and current density. This work provides a novel catalyst design showing the potential for the practical application of electrochemical reduction of CO2.

Oxygen vacancy-induced modulation of the built-in electric field of TiO2-α/WO3-δ for enhanced CO2 photoreduction

Inefficient light absorption and rapid charge recombination pose significant challenges in limiting the efficacy of CO2 photoreduction. In this work, we developed TiO2-α/WO3-δ heterojunctions with precisely tunable oxygen vacancies (OVs) as a catalyst for photocatalytic CO2 reduction to CO. The TiO2-α/WO3-δ heterojunction demonstrated remarkable performance, yielding 28.11 μmol g−1 h−1 of CH4 and 22.19 μmol g−1 h−1 of CO, representing 18.6-fold and 3.9-fold increases, respectively, compared to unreduced samples. The introduction of OVs creates a new defect energy level in the photocatalyst, inducing localized electron enrichment. This modulates the bandgap and enhances the built-in electric field (BEF) intensity. The optimized bandgap expands the light absorption range, while the enhanced BEF effectively suppresses carrier recombination, collectively improving the photocatalytic CO2 reduction activity.

Z-scheme heterojunctions of NF@ZnO/0.5CeO2 monolithic catalyst for photothermal catalytic CO2 reduction under concentrated solar irradiation

Z-scheme heterojunctions of NF@ZnO/0.5CeO2 monolithic catalyst for photothermal catalytic CO2 reduction under concentrated solar irradiation

Atomic cerium-doped CuOx catalysts for efficient electrocatalytic CO2 reduction to CH4

Copper (Cu) is widely used in the electrochemical carbon dioxide reduction reaction (ECO2RR) for efficient methane (CH4) product. However, the morphology and valence of Cu-based catalysts are usually unstable under reaction conditions. In this work, we prepared Ce-doped MOF-199 precursor (Ce/HKUST-1) and further obtained nanoparticle electrocatalyst Ce/CuOx-NPs by cyclic voltammetry (CV) pretreatment. The Faradic efficiency of methane (FECH4) maintains above 62% within a broad potential window of 350 mV and the maximum FECH4 reaches 67.4% with a partial current density of 293 mA/cm2 at −1.6 V vs. a reversible hydrogen electrode. Catalyst characterization and theoretical calculations revealed that the unique electronic structure and large ionic radius of Cerium (Ce) not only promoted the generation of key intermediate *CO but also lowered energy barrier of the *CO to *CHO step. This study provides a novel and efficient catalyst for methane production in ECO2RR and offers profound insights into constructing high performance Cu-based catalysts.

Barium titanate photocatalysts with silver-manganese dual cocatalyst for carbon dioxide reduction with water.

Titanate photocatalysts with suitable cocatalysts are promising candidates for photocatalytic CO2 reduction, with the use of water as an electron donor. Here, several barium titanates with various compositions were examined, and BaTi4O9 (BT4) was found to be the best photocatalyst with the assistance of an Ag cocatalyst for photocatalytic CO2 reduction to form CO. The photocatalytic activity was further enhanced by the use of MnOx as an additional cocatalyst to construct an Ag-MnOx/BT4 photocatalyst, where Ag and MnOx were selectively deposited at different facets on BT4 crystal and functioned as active sites for CO2 reduction and water oxidation, respectively. As for the oxidative products from water, molecular oxygen (O2) and hydrogen peroxide (H2O2) were obtained.

Bifunctional Catalysts for CO2 Reduction and O2 Evolution: A Pivotal for Aqueous Rechargeable Zn-CO2 Batteries.

The quest for the advancement of green energy storage technologies and reduction of carbon footprint is determinedly rising toward carbon neutrality. Aqueous rechargeable Zn-CO2 batteries (ARZCBs) hold the great potential to encounter both the targets simultaneously, i.e., green energy storage and CO2 conversion to value-added chemicals/fuels. The major descriptor of ARZCBs efficiency is allied with the reactions occurring at cathode during discharging (CO2 reduction) and charging (O2 evolution) which own different fundamental mechanisms and hence mandate the employment of two different catalysts. This presents an overall complex and expensive battery system which requires a concrete solution, while the development and application of a bifunctional cathode catalyst toward both reactions could reduce the complexity and cost and thus can be a pivotal for ARZCBs. However, despite the increasing research interest and ongoing research, a systematic evaluation of bifunctional catalysts is rarely reported. In this review, the need of bifunctional cathode catalysts for ARZCBs and associated challenges with strategies have been critically assessed. A detailed progress examination and understanding toward designing of bifunctional catalyst for ARZCBs have been provided. This review will enlighten the future research approaching boosted performance of ARZCBs through the development of efficient bifunctional cathode catalysts.

Covalent Organic Framework with Donor1‐Acceptor‐Donor2 Motifs Regulating Local Charge of Intercalated Single Cobalt Sites for Photocatalytic CO2 Reduction to Syngas

AbstractCovalent organic framework (COF) has attracted increasing interest in photocatalytic CO2 reduction, but it remains a challenge to achieve high conversion efficiency owing to the insufficient active site and fast charge recombination. Rationally optimizing the electronic structures of COF to regulate the local charge of active sites precisely is the key point to improving catalytic performance. Herein, intercalated single Co sites coordinated by imine‐N motifs have been designed by using trinuclear copper‐based imine‐COFs with distinct electronic moieties via a molecular engineering strategy. It is confirmed that the charge delivery property and local charge distribution of these heterometallic frameworks can be profoundly influenced by electronic structures. Among these featured structures with mixed‐state copper clusters, Co/Cu3‐TPA‐COF stands out for an exceptional photocatalytic CO2 reduction activity and tunable syngas (CO/H2) ratio by changing various bipyridines. Experimental and theoretical results indicate that interlayer Co‐imine N motifs on the donor1‐acceptor‐donor2 structures facilitate the formation of a highly separated electron‐hole state, which effectively induces the oriented electron transfer from dual electron donors to Co centers, achieving an enhanced CO2 activation and reduction. This work opens up an avenue for the design of high‐performance COF‐based catalysts for photocatalytic CO2 reduction.

Covalent Organic Framework with Donor1-Acceptor-Donor2 Motifs Regulating Local Charge of Intercalated Single Cobalt Sites for Photocatalytic CO2 Reduction to Syngas.

Covalent organic framework (COF) has attracted increasing interest in photocatalytic CO2 reduction, but it remains a challenge to achieve high conversion efficiency owing to the insufficient active site and fast charge recombination. Rationally optimizing the electronic structures of COF to regulate the local charge of active sites precisely is the key point to improving catalytic performance. Herein, intercalated single Co sites coordinated by imine-N motifs have been designed by using trinuclear copper-based imine-COFs with distinct electronic moieties via a molecular engineering strategy. It is confirmed that the charge delivery property and local charge distribution of these heterometallic frameworks can be profoundly influenced by electronic structures. Among these featured structures with mixed-state copper clusters, Co/Cu3-TPA-COF stands out for an exceptional photocatalytic CO2 reduction activity and tunable syngas (CO/H2) ratio by changing various bipyridines. Experimental and theoretical results indicate that interlayer Co-imine N motifs on the donor1-acceptor-donor2 structures facilitate the formation of a highly separated electron-hole state, which effectively induces the oriented electron transfer from dual electron donors to Co centers, achieving an enhanced CO2 activation and reduction. This work opens up an avenue for the design of high-performance COF-based catalysts for photocatalytic CO2 reduction.

Investigation of m- and p-xylene linked bimetallic Ni-cyclam-complexes as potential electrocatalysts for the CO2 reduction

Among the various molecular CO2 reduction catalysts, the [Ni(cyclam)]2+ (Ni-{N4}) complex with its earth-abundant metal center and macrocyclic ligand proved to be efficient for the selective electrochemical conversion of CO2 to CO. In the present study we now connected the two Ni-cyclam units by using para- and meta-xylene as organic linkers attached to the amines of the macrocycle to form the p-{Ni2} andm-{Ni2} complexes, respectively, and test them as catalysts for the electrochemical CO2 reduction reactions. Notably, the p-{Ni2} complex demonstrates a higher faraday efficiency in the electrochemical reduction of CO2 to CO compared to the m-{Ni2} complex. This finding highlights the significant role played by the M-M distance in influencing this catalytic process.

One-Step synthesis of nanosized Cu-Ag films using atmospheric pressure plasma jet

Thin films of copper-silver (Cu-Ag) composed of nanosized particles were successfully synthesised and deposited on glass and carbon substrates under various metal ratios in a single step using an atmospheric pressure plasma jet (APPJ) system. This rapid synthesis and deposition technique only requires very low power input (20 W) and rudimentary solutions of metal salt precursors and DI water without additives, pretreatment, or post-treatment process. Successful Cu-Ag alloying was observed, with excellent compositional and deposition area control. Strongly adherent films can be formed on conductive and non-conductive substrate, making APPJ an ideal and sustainable approach for large-scale deposition of multi-component thin metallic films. A comprehensive characterisation of Cu-Ag alloys deposited using APPJ and their potential use as electrocatalytic CO2 reduction catalysts is discussed.

The temperature dependence of electrochemical CO2 reduction on Ag and CuAg alloys

Ag is often studied as catalyst for electrochemical CO2 reduction as it shows high selectivity towards CO and is easily alloyed with Cu to enhance performance using CuAg catalysts. In this study, we investigated the effect of temperature on Ag and CuAg catalysts and compare these with previous results on Au and Cu catalysts. We show that the temperature effect is complicated as it shows an interplay with CO2 concentration, potential and mass transport. It is therefore crucial to deconvolute these parameters and study the effect of temperature under different conditions. Moreover, we show that alloying Ag with Cu can inhibit some of the deactivation effects observed at high temperatures on pure Cu. CuAg alloys can prevent the dominance of hydrogen evolution at elevated temperatures, although an optimum of C2+ products with temperature is still observed.