CO2 Photoreduction Research Articles

Dual‐Site NiO/Bi3O4Br Heterojunction Catalyst for High‐Efficiency CO2‐to‐CH4 Conversion

AbstractSolar light‐driven conversion of CO2 into chemicals with high calorific value is regarded as an upcoming carbon utilization technology for alleviating the energy crisis. This technique faces the challenge of low CO2 conversion and product yield due to charge recombination in the catalyst. In this paper, a dual‐reaction site heterojunction catalyst was designed and fabricated by combining NiO with Bi3O4Br nanosheets, for the separation of CO2 reduction and H2O oxidation semireactions, which effectively promoted electrons and holes separation. The resulting catalyst exhibited a high CH4 production rate (8.12 µmol/g) and selectivity (94.69%). Electron distribution and band structure were investigated to explain the satisfactory catalytic performance. In addition, combining the in‐situ DRIFTS results, a formic acid‐intermediated CO2‐to‐CH4 reaction pathway was proposed. This work aims to pave the way for CH4 production via CO2 photoreduction with high efficiency and selectivity.

Enabling Interfacial Lattice Matching by Selective Epitaxial Growth of CuS Crystals on Bi2WO6 Nanosheets for Efficient CO2 Photoreduction into Solar Fuels

AbstractPhotocatalytic CO2 reduction serves as an important technology for value‐added solar fuel production, however, it is generally limited by interfacial charge transport. To address this limitation, a two‐dimensional/two‐dimensional (2D/2D) p‐n heterojunction CuS‐Bi2WO6 (CS‐BWO) with highly connected and matched interfacial lattices was designed in this work via a two‐step hydrothermal tandem synthesis strategy. The integration of CuS with BWO created a robust interface electric field and provided fast charge transfer channels due to the work function difference, as well as highly connected and matched interfacial lattices. The p‐n heterojunction combination promoted the electron transfer from the Cu to Bi sites, leading to the coordination of Bi sites with high electronic density and low oxidation state. The Bi sites in the BWO nanosheets facilitated the adsorption and activation of CO2, and the generation of high‐coverage key intermediate b‐CO32−, while CuS (CS) acted as a broad light‐harvesting material to provide abundant photoinduced electrons that were injected into the conduction band of BWO for CO2 photoreduction reaction. Remarkably, the p‐n heterojunction CS‐BWO exhibited average CO and CH4 yields of 33.9 and 16.4 μmol g−1 h−1, respectively, which were significantly higher than those of CS, BWO, and physical mixture CS‐BWO samples. This work provided an innovative design strategy for developing high‐activity heterojunction photocatalyst for converting CO2 into value‐added solar fuels.

Prolonging Charge Carrier lifetime via Intraband Defect Levels in S-scheme Heterojunctions for Artificial Photosynthesis.

S-scheme heterostructure photocatalysts, distinguished by unique charge-transfer pathways and exceptional catalytic redox capabilities, have found widespread applications in addressing challenging chemical processes, including the photocatalytic reduction of CO2 with a high reaction barrier. Nevertheless, the influence of intraband defect levels within S-scheme heterojunctions on charge separation, carrier lifetime, and surface catalytic reactions has, for the most part, been overlooked. Herein, we develop a tunable defect-level-assisted strategy to construct an electron reservoir, effectively prolonging the lifetime of charge carriers through the rapid capture and gradual release of photoelectrons within WO3-x/In2S3 S-scheme heterojunctions, as authenticated by femtosecond transient absorption spectroscopy and theoretical simulations. The surface photoredox mechanism, unraveled by Gibbs free energy calculations, demonstrates that oxygen-vacancy-induced defect states in WO3-x/In2S3 heterojunctions unlock the rate-determining H2O oxidation into free oxygen molecules by forming metastable oxygen intermediates, contributing to the facilitation of H2O photooxidation. This distinct role, combined with the extended carrier lifetime, results in boosted CO2 photoreduction with nearly 100% CO selectivity in the absence of any photosensitizer or scavenger. Our work sheds light on the role of controllable defect levels in governing charge transfer dynamics within S-scheme heterojunctions, thereby inspiring the development of more advanced photocatalysts for artificial photosynthesis.

Molecular catalyst coordinatively bonded to organic semiconductors for selective light-driven CO2 reduction in water.

The selective photoreduction of CO2 in aqueous media based on earth-abundant elements only, is today a challenging topic. Here we present the anchoring of discrete molecular catalysts on organic polymeric semiconductors via covalent bonding, generating molecular hybrid materials with well-defined active sites for CO2 photoreduction, exclusively to CO in purely aqueous media. The molecular catalysts are based on aryl substituted Co phthalocyanines that can be coordinated by dangling pyridyl attached to a polymeric covalent triazine framework that acts as a light absorber. This generates a molecular hybrid material that efficiently and selectively achieves the photoreduction of CO2 to CO in KHCO3 aqueous buffer, giving high yields in the range of 22 mmol g-1 (458 μmol g-1 h-1) and turnover numbers above 550 in 48 h, with no deactivation and no detectable H2. The electron transfer mechanism for the activation of the catalyst is proposed based on the combined results from time-resolved fluorescence spectroscopy, in situ spectroscopies and quantum chemical calculations.

Silver Nanoparticle‐Embedded Zirconium‐Based Metal‐Organic Framework for Photoreduction of Carbon Dioxide to Acetic Acid in Aqueous Medium

AbstractCatalytic conversion of CO2 into value‐added chemicals is necessary to mitigate the increasing global warming and energy‐related issues. The selective production of C2 or C2+ products by photoreduction of CO2 is a challenging task due to the sluggish kinetics of C─C coupling. Herein, the potential of a silver nanoparticle (Ag NP) incorporated metal‐organic framework (MOF), NU‐1000 is introduced, to harvest light and ease the uphill electron transfer. The growth of silver nanoparticles on thiol‐functionalized NU‐1000 is studied using the atomic pair distribution function (PDF) analysis. The C2 product formed using Ag@NU‐1000‐SH without any sacrificial agents is acetic acid, which is confirmed by 1H‐NMR and HRMS data. The catalyst displays a high acetate output of 293.58 µmolg−1h−1 with a selectivity of 79.4%. The XPS and DFT calculations evidence that the presence of the charge‐polarised states in the as‐synthesized catalyst act as asymmetric centers that favor the C─C coupling reaction. The combined experimental (in situ DRIFT spectroscopic studies) and theoretical calculations reveal that the C─C coupling takes place via the coupling of COOH*intermediates.

Dual Active Sites with Charge‐asymmetry in Organic Semiconductors Promoting C−C Coupling for Highly Efficient CO2 Photoreduction to Ethanol

AbstractSelective CO2 photoreduction into high‐energy‐density and high‐value‐added C2 products is an ideal strategy to achieve carbon neutrality and energy shortage, but it is still highly challenging due to the large energy barrier of the C−C coupling step and severe exciton annihilation in photocatalysts. Herein, strong and localized charge polarization is successfully induced on the surface of melon‐based organic semiconductors by creating dual active sites with a large charge asymmetry. Confirmed by multiscale characterization and theoretical simulations, such asymmetric charge distribution, originated from the oxygen dopants and nitrogen vacancies over melon‐based organic semiconductors, reduces exciton binding energy and boosts exciton dissociation. The as‐formed charge polarization sites not only donate electrons to CO2 molecules but also accelerate the coupling of asymmetric *CO*CO intermediates for CO2 photoreduction into ethanol by lowering the energy barrier of this process. Consequently, an exceptionally high selectivity of up to 97 % for C2H5OH and C2H5OH yield of 0.80 mmol g−1 h−1 have been achieved on this dual active sites organic semiconductor. This work, with its potential applicability to a variety of non‐metal multi‐site catalysts, represents a versatile strategy for the development of advanced catalysts tailored for CO2 photoreduction reactions.

High‐Selectivity Tandem Photocatalytic Methanation of CO2 by Lacunary Polyoxometalates‐Stabilized *CO Intermediate

AbstractStabilizing specific intermediates to produce CH4 remains a main challenge in solar‐driven CO2 reduction. Herein, g‐C3N4 is modified with saturated and lacunary phosphotungstates (PWx, x=12, 11, 9) to tailor the CO2 reduction pathway to yield CH4 in high selectivity. Increased lacuna of phosphotungstates leads to higher CH4 yield and selectivity, with a superior CH4 selectivity of 80 % and 40.8 μmol ⋅ g−1 ⋅ h−1 evolution rate for PW9/g‐C3N4. Conversely, g‐C3N4 and PWx alone show negligible CH4 production. The conversion of CO2 to CH4 follows a tandem catalytic process. CO2 is initially activated on g‐C3N4 to form *CO intermediates, meanwhile photogenerated electrons derived from g‐C3N4 transfer to PWx. Then the reduced PWx captures *CO, which is subsquently hydrogenated to CH4. With the injection of two photogenerated electrons, PW9 is capable of adsorbing and activating *CO. However, the reduced PW12 and PW11 are incapable of adsorbing *CO due to the small energy of occupied molecular orbitals, which is the reason for the poorer activity of PWx/g‐C3N4 (x=12, 11) compared with that of PW9/g‐C3N4. This work provides new insights to regulate highly selective CO2 photoreduction to CH4 by utilizing lacuna of polyoxometalates to enhance the interaction of metals in polyoxometalates with key intermediates.

Efficient UV-Vis-NIR Responsive CO2 Reduction Photocatalyst with Black Pinecone-Shaped Carbon Nitride Loaded with Lanthanum Oxide.

Photothermal catalysis combines the advantages of photocatalysis and thermal activation, which provides a new research angle for CO2 catalytic reduction. In this study, Black carbon nitride with a three-dimensional (3D) pinecone-shaped structure (BPCN) was prepared by a simple solvothermal method using melamine as a precursor without the aid of a template. Lanthanum oxide doping on the BPCN catalysts (BPCN-La) was achieved by ultrasonic impregnation. This unique pinecone-shaped structure consists of self-assembled and interlaced carbon nitride rods (by SEM). The lanthanum element was distributed on the surface of the CN framework in the form of La2O3 (by XPS). The chemical structures of the samples were characterized by solid-state 13C nuclear magnetic resonance (13C NMR) and elaborated by density functional theory (DFT) analysis. This black carbon nitride expanded the light absorption band edge into the near-infrared (NIR) (300-1400 nm, by UV-vis absorption spectra) and had excellent photothermal conversion activity. La atom doping can significantly boost photogenerated electron excitation (by photocurrent test) and promote carrier separation and transfer (by PL). Upon incorporation of La atoms into BPCN, the highest occupied molecular orbital (HOMO) orbital is more concentrated on the oxygen atoms of La2O3. BPCN-La considerably narrowed the band gap width, exhibited an exceptional photothermal effect, and provided a large surface area, which significantly enhanced the photocatalytic reduction of CO2 reactions. The yields of CO reached 58.2 and 104.9 μmol·h-1·g-1 for BPCN and BPCN-La, respectively, with GCN as the control (6.3 μmol·h-1·g-1). Theoretical reaction pathways and selectivity for the photoreduction of CO2 on BPCN and BPCN-La were studied by DFT simulation. This work provides a new vision for the design of photothermal synergistic without extra-thermal input and full spectral response photocatalysts with high efficiency.

Gas Phase CO2 Photoreduction Behaviors over Composites of Galvanostatically Pulse‐Deposited Cu2O Nanoparticles and Anodized TiO2 Nanotube Arrays

Electrochemically synthesized composites of vertically aligned titanium dioxide (TiO2) nanotube arrays (TNAs) and cuprous oxide (Cu2O) nanoparticles (CNPs) are used for studying gas phase CO2 photoreduction behaviors. Anodized TNA surfaces with an average aperture size of 60 nm are decorated with CNPs using galvanostatic pulse electrodeposition. The nucleation and growth of CNPs are investigated with the help of cyclic voltammetry and potential‐time transients. The number of CNPs and their distribution on TNA surfaces are widely altered by adjusting the ON/OFF time, the number of applied current pulse, and the bath temperature. After characterizing structural and physical properties of the prepared CNPs/TNAs samples, in situ observation of CO2 photoreduction in gas phase over CNPs/TNAs is carried out in a high vacuum. The enhancement in CO2 photoreduction over CNPs/TNAs samples is observed for the optimized size and the number of CNPs on TNAs. The reaction route of the same is ascertained from the reaction products. The experimental results indicate that the size of CNPs should be comparable to the average pore size of TNAs for promoting CO2 photoreduction, and the relationship between CO2 photoreduction and the structural properties of CNPs is further discussed.

Engineering Dual-Defective 0D/2D VN-CNQDs/VBi-Bi4O5Br2 S-Scheme Heterostructure for Boosting CO2 Photoreduction in Air.

The direct photocatalytic reduction of CO2 in air is the future trend of photocatalyst application. Herein, the 0D carbon nitride quantum dots with nitrogen vacancies (VN-CNQDs) and 2D bismuth-deficient Bi4O5Br2 (VBi-Bi4O5Br2) are integrated by hydrothermal method. The S-scheme heterostructure of VN-CNQDs/VBi-Bi4O5Br2 composite promotes the separation rate of photogenerated carriers and enhances the redox capacity. The dual defects provide a large number of adsorption and catalytic sites that enhance the ability to capture and reduce CO2. The synergistic effect of S-scheme heterostructure and defect engineering enables the efficiency of CO2 photoreduction to CO with VN-CNQDs/VBi-Bi4O5Br2 to reach 16.89µmolg-1h-1 in air and 55.69µmolg-1h-1 in VCO2: VAir = 3:1 condition, which is 17 and 21 times higher than that of Bi4O5Br2, respectively. The dual-defective VN-CNQDs/VBi-Bi4O5Br2 exhibits more lower energy barrier for forming *CO2, *COOH, and *CO and is easier to release CO gas. And it exhibits excellent cycling stability for photocatalytic CO2 reduction to CO. The photocatalytic reduction mechanism of CO2 to CO in the VN-CNQDs/VBi-Bi4O5Br2 S-scheme heterostructure is further analyzed. This work provides new perspectives for the design of the photocatalysts with defect engineering for efficient photoconversion at low CO2 concentrations.

Structurally Asymmetric Ni‐O‐Mn Node in Metal‐Organic Layers on Carbon Nitride Support for CO2 Photoreduction

The Jahn‐Teller (J‐T) effect‐induced lattice distortion presents an advantageous approach to tailor the electronic structure and CO2 adsorption properties of catalytic centers, consequently conferring desirable photocatalytic CO2 reduction activity and selectivity. Nevertheless, achieving precise J‐T distortion control over catalytic sites to enhance CO2 adsorption/activation and target‐product desorption remains a formidable challenge. In this work, we successfully induced J‐T lattice distortion in neighboring Ni sites by exchanging high‐spin Mn2+ into Ni‐O‐Ni nodes. EXAFS results and DFT simulations revealed that the highly asymmetric Ni‐O‐Mn nodes induced structural contraction (shortened Ni‐O bonds) in the adjacent Ni‐O lattice. The magnetic hysteresis loop (M‐H) confirmed that the introduction of Mn2+ increased the number of spin electrons, thereby increasing the magnetization intensity. The spin mismatch between photogenerated electrons and holes suppressed charge recombination. Significantly, the d orbitals of the Ni sites in the Ni‐O‐Mn nodes exhibited strong orbital hybridization with the p orbitals of CO2, as evidenced by the enhanced d‐p orbital overlap, facilitating rapid CO2 adsorption and activation. Consequently, the sample featuring lattice‐mismatched Ni‐O‐Mn nodes exhibited an 8.79‐fold enhancement in CO production rate compared to the Ni‐O‐Ni nodes, in the absence of cocatalysts and sacrificial reagents.

Structurally Asymmetric Ni-O-Mn Node in Metal-Organic Layers on Carbon Nitride Support for CO2 Photoreduction.

The Jahn-Teller (J-T) effect-induced lattice distortion presents an advantageous approach to tailor the electronic structure and CO2 adsorption properties of catalytic centers, consequently conferring desirable photocatalytic CO2 reduction activity and selectivity. Nevertheless, achieving precise J-T distortion control over catalytic sites to enhance CO2 adsorption/activation and target-product desorption remains a formidable challenge. In this work, we successfully induced J-T lattice distortion in neighboring Ni sites by exchanging high-spin Mn2+ into Ni-O-Ni nodes. EXAFS results and DFT simulations revealed that the highly asymmetric Ni-O-Mn nodes induced structural contraction (shortened Ni-O bonds) in the adjacent Ni-O lattice. The magnetic hysteresis loop (M-H) confirmed that the introduction of Mn2+ increased the number of spin electrons, thereby increasing the magnetization intensity. The spin mismatch between photogenerated electrons and holes suppressed charge recombination. Significantly, the d orbitals of the Ni sites in the Ni-O-Mn nodes exhibited strong orbital hybridization with the p orbitals of CO2, as evidenced by the enhanced d-p orbital overlap, facilitating rapid CO2 adsorption and activation. Consequently, the sample featuring lattice-mismatched Ni-O-Mn nodes exhibited an 8.79-fold enhancement in CO production rate compared to the Ni-O-Ni nodes, in the absence of cocatalysts and sacrificial reagents.

Self-Assembly Synthesis of Oxygen and Sulfur Co-Doped Porous Graphitic Carbon Nitride Nanosheets for Boosting CO2 Photoreduction.

Graphitic carbon nitride (CN) has garnered considerable attention in the field of visible-light CO2 photoreduction, but its efficiency remains limited by the intrinsic π-conjugated skeleton. Here, O and S were co-doped CN (O, S/CN) by a facile "hydrolysis + calcination" approach to modulate the physicochemical and electronic structure. Distinctive from S doped CN (SCN), O, S/CN owned porous layer structure with several nanosheets and less SO4 2- groups on the surface. The amount of heteroatom-doping was achieved by changing the hydrothermal temperature. The optimum O, S/CN-80 achieved moderate CO production rate of 1.29 μmol g-1 h-1, which was 3.79 times as much as SCN (0.34 μmol g-1 h-1). The O and most S atoms were substitutionally doped and the effect of S doped state on the improved efficiency of CO generation in O, S/CN was also explored based on the theoretical calculations. This work provides an inspiration to develop efficient dual-doped CN photocatalysts for photocatalytic CO2 reduction.

Lattice energy transfer from homo-crystalline substitution for enhanced piezo-photocatalytic CO2 conversion

The rapid recombination of carriers and large activation energy of CO2 compromise the efficiency of CO2 photoreduction. Herein, SrTiO3 (STO) with different molar ratios of La3+ and Al3+ double-site homo-crystalline substitution is prepared by a ball-milling molten salt method. The concentration of Ti3+ and excess oxygen vacancies decrease to improve the catalytic activity. Meanwhile, the double sites act as electron transfer platforms for easy electron transfer from the bulk phase to the surface to foster CO2 photoreduction. Not only that, the energy transfer due to doping-induced lattice distortion can potentially enhance the photocatalytic activity. A piezoelectrically polarized electric field is introduced to further expedite charge transport. As a result, the activity of La, Al-STO piezo-photocatalytic CO2 reduction is improved to 39.17 µmol g-1h−1, which is more than seven times better than that of the pure STO. Furthermore, CO2 adsorbs spontaneously on the catalysts because the thermodynamic energy barrier decreases due to the piezoelectric force, which is verified by density-functional theory calculation. This study reveals the great potential of double-site homo-crystalline substitution of STO pertaining to the charge transport kinetics and thermodynamics of the catalytic reaction in the piezo-photocatalytic CO2 process.

Slow-light-driven photocatalytic CO2 reduction to CH4 mediated by photonic crystal Graphdiyne-Cu/ZnO Z-scheme system

Developing photocatalysts with high activity and selectivity remains a significant challenge in the field of CO2 photoreduction for producing valuable chemical or fuel products under mild conditions. Herein, photonic crystal (PC) GDY-Cu/ZnO was constructed through the in-situ induced growth of graphdiyne (GDY) on PC Cu/ZnO surface via H2-reduction for efficient photoreduction of CO2 to CH4. With the aid of photonic crystal structure, PC GDY-Cu/ZnO exhibits a distinctive red-edge slow light region which can significantly improve the utilization efficiency of visible light and intensify photo-catalysis. Additionally, the formed all-solid-state Z-scheme system efficiently accelerates photoelectron migration, facilitating e-/h+ separation. Thirdly, the surface GDY, along with the enrich oxygen vacancies generated during H2 reduction, enhances the adsorption and activation toward CO2 and H2O on PC GDY-Cu/ZnO interface. In consequence, PC GDY-Cu/ZnO demonstrates highly photocatalytic conversion of CO2 to CH4, achieving a CH4 yield of 33.67 μmol·g−1·h−1 with 93.3 % selectivity via slow-light-driven photocatalysis CO2 reduction. This work provides an efficient strategy to modify ZnO for the efficient photoreduction of CO2 to CH4.

An anthryl-modified bis(terpyridine)zinc(II) complex for improved CO2 photoreduction

An anthryl-modified bis(terpyridine)zinc(II) complex for improved CO2 photoreduction

In-situ preparation of BiOBr/Bi-doped CsPbBr3 S-scheme heterojunction for efficient photocatalytic CO2 reduction

Metal halide perovskite nanocrystals have garnered significant attention in the realm of photocatalytic CO2 reduction in recent years owing to their remarkable reducing properties and high selectivity. However, the issue of low photocatalytic activity due to severe carrier recombination phenomena in perovskite has posed a significant challenge. To address this, a one-pot in-situ preparation strategy was employed to create a BiOBr/Bi-doped perovskite nanocrystal S-scheme heterojunction, resulting in a significant improvement in the CO2 photoreduction performance. The heterojunction material exhibited a CO yield of 151.56 μmolg-1h−1, with a selectivity for CO of 93.6 %. The molar ratio of the components was modulated using an in-situ water aging strategy, yielding a photocatalyst performance that exceeded that of pure BiOBr. The synthesis strategy of one-step in-situ preparation of heterojunctions overcomes the problem of insufficient bonding caused by two-step methods. And various characterizations and DFT calculations strongly support the S-scheme mechanism of the photocatalyst. The active site effectively reduces the energy barrier for the transition from *COOH to *CO intermediate, thereby significantly improving photocatalytic activity.

A robust floating oxygen-doped graphitic carbon nitride sheet for efficient photocatalytic CO2 conversion

Photocatalytic CO2 reduction offers a promising approach for converting CO2 into valuable chemicals. However, typical conversion systems suffer from inefficient CO2 mass transfer and complex recycling processes. In this study, we developed a floating sheet as a robust photocatalytic CO2 conversion system by integrating graphitic carbon nitride (CN) nanosheets onto polytetrafluoroethylene (PTFE) fiber membrane, followed by oxygen (O) doping into the CN (CN-O) via oxygen-plasma treatment. The floatable CN-O/PTFE sheet exhibits slight wettability in water under 0.25 MPa of CO2 pressure in our reactor system, facilitating the delivery of dissolved CO2 to the CN-O photocatalyst surface. O-doping enhances the visible light absorption and improves the separation and transport efficiency of photogenerated electrons and holes due to O-doping-induced states in CN. Consequently, the floating CN-O/PTFE system achieves an exceptional photocatalytic CO2 conversion rate of 102.3 μmol g-1h−1, approximately 4.8 times higher than a conventional CN-powder dispersion system in water. Moreover, the sheet demonstrates excellent cycling durability, with no significant exfoliation of the catalytic layer or reduction in CO2 photoreduction activity after 20 consecutive cycles. This study presents a novel approach to designing photocatalytic systems for efficient CO2 conversion.

Metallic engineering in metal-porphyrin frameworks for highly efficient CO2 photoreduction

Metallic engineering in metal-porphyrin frameworks for highly efficient CO2 photoreduction

MOF-derived phase-selective synthesis of ln2O3 with appropriate surface atomic arrangement for CO2 photoreduction

Crystal phase engineering emerges as a powerful strategy to enhance photocatalytic activity, yet controlled phase-selective synthesis and phase-dependent performance understanding remain challenging. In this study, we introduce a novel method for synthesizing phase-engineered In2O3 via the pyrolysis of metal–organic frameworks (MOFs). We demonstrate that the functional groups and pyrolysis temperatures of MOFs are critical for phase-selective synthesis. Specifically, pyrolysis of MIL-68(ln)–NH2 at optimal temperatures yields In2O3 with rhombohedral (rh-In2O3), cubic (c-In2O3), and rhombohedral/cubic heterophase (rh/c-In2O3) structures. Our photocatalytic CO2 reduction tests reveal that c-In2O3 outperforms rh-In2O3 and rh/c-In2O3, achieving a CO production rate of 29.19 μmol g-1h−1 with 94.47 % selectivity. Spectroscopic and theoretical analyses show that c-In2O3 has superior charge transfer efficiency and lower reaction energy barriers, particularly for the rate-determining *CO intermediate, which exhibits a lower Gibbs free energy on its surface. This work provides a significant advancement in optimizing photocatalytic CO2 reduction efficiency through precise phase engineering, underscoring the vital role of phase control in enhancing catalytic performance.