CO2 Adsorption Research Articles

Utilization of cocoa pod husk waste biomass for post-combustion CO2 adsorption

Biomass-derived activated carbon for carbon dioxide (CO2) post-combustion has been drawing attention because they are cost-effective and environment-friendly. In this study, activated carbon was prepared from cocoa pod husk waste (COP) biomass for CO2 adsorption. The COP was pyrolyzed and activated using potassium hydroxide (KOH). The activated carbon prepared was characterized using scanning electron microscopy (SEM), Scanning Electron Microscopy- Energy Dispersive Spectroscopy and Fourier transform infrared spectroscopy (FTIR) analysis. The performance of the activated carbons prepared for CO2 was evaluated using a CO2 gas analyzer. Optimization of the adsorption process of CO2 was carried out by varying some important variables affecting the adsorption process. Results showed activated carbon prepared has a good pore structure with high carbon content that supported CO2 adsorption. The Freundlich model provided the best fit with the experimental data while data fitted well to pseudo-second-order kinetics with an adsorption capacity of 6.5 mg/g. The optimal condition for CO2 adsorption, was an adsorption time of 1 min, a Carbonization temperature of 700 °C, and Bed height of 5 cm, and % CO2 removal of 99.5%. The study revealed (COP) biomass as a suitable activated carbon precursor for CO2 capture.

Characterizing the surface compositions of supported bimetallic PtSn clusters: Effects of cluster-support interactions and surface adsorbates

PtSn bimetallic clusters on TiO2(110) and highly oriented pyrolytic graphite (HOPG) surfaces have been characterized by scanning tunneling microscopy, low energy ion scattering (LEIS), X-ray photoelectron spectroscopy, and temperature programmed desorption (TPD); density functional theory (DFT) calculations have also been performed to better understand adsorption of CO and D2 on the PtSn surfaces. On TiO2 at coverages of 2 ML of Pt and 2 ML of Sn, exclusively bimetallic clusters are formed for both orders of deposition because clusters of the first metal completely cover the surface such that all atoms of the second metal are incorporated into the existing clusters. In contrast, on HOPG, the high mobility and weak cluster-support interactions on HOPG result in much larger 2 ML monometallic clusters (∼30 Å high) that do not completely cover the surface, and deposition of the second metal produces larger clusters as well as smaller ones. Despite the difference in cluster morphologies for the different orders of deposition and supports, the LEIS experiments demonstrate that in all cases, the PtSn clusters are rich in Sn at the surface, as expected based on the lower surface free energy for Sn compared to Pt. Furthermore, the +0.2 eV shift in the Sn(3d5/2) binding energy observed on all surfaces in the presence of Pt is consistent with PtSn alloy formation. Deposition of 2 ML of Sn on TiO2 produces two-dimensional clusters with oxidation of Sn and reduction of titania at the cluster-support interface, but addition of Pt to the Sn clusters causes Sn to diffuse away from this interface, leaving Sn in the metallic state. TPD experiments on 2 ML Pt/TiO2 with increasing coverages of Sn show that the number of adsorption sites for D2 sharply decreases to nearly zero at 0.5 ML, while CO adsorption decreases to zero only at much higher Sn coverages of 2 ML. DFT studies for Sn modified Pt surfaces and bulk structures demonstrate that for CO adsorption at low Sn coverages (≤0.25 ML), the strong Pt-CO interactions induce diffusion of Pt to the cluster surface and the formation of a bulk Pt3Sn alloy, whereas D2 adsorption does not lead to interactions with the Pt surface that are strong enough to induce alloy formation. A single Sn adatom prevents D2 adsorption on four neighboring Pt atoms via site-blocking and the donation of electron density to Pt.

Development of efficient CO2 adsorbents: Synthesis and performance evaluation of dopamine-modified halloysite nanotubes loaded with ZIF-8

Carbon capture, utilization, and storage (CCUS) is a crucial technology for achieving carbon reduction targets. The key to CCUS technology lies in developing and designing efficient and low-cost CO2 capture materials. Metal-organic frameworks (MOFs) have emerged as promising CO2 adsorbents in the field of carbon capture. However, high agglomeration of nanoparticles and high cost have severely hindered the application of MOF-based solid adsorbents. This study employs an in-situ growth method to prepare a novel “corncob-shaped” PHNT@ZIF-8 composite material. During the reaction process, surface modification of halloysite nanotubes (HNT) enhances the interaction between HNT and ZIF-8. The resulting PHNT@ZIF-8 exhibits an enhanced CO2 adsorption capacity of 1.48 mmol/g. Notably, the functionalized PHNT@ZIF-8 as CO2 adsorbents demonstrated significant adsorption properties: a high specific surface area of 409.74 m2/g, good selectivity in simulated flue gas composition of 15%/85% (CO2/N2) (39.1), excellent thermal stability, and superior regenerability. Moreover, PHNT@ZIF-8 adsorbs CO2 primarily through van der Waals forces, which involve low energy and are easily reversible. After eight adsorption–desorption cycles, CO2 capacity retention rate remains as high as 93% (1.37 mmol/g). This work enriches the repertoire of solid CO2 composite adsorbents, providing a novel pathway for enhancing CO2 adsorption performance.

Modulating the electronic interaction of ZnFemCrOx/SAPO-34 to boost CO2 hydrogenation to light olefins

Hydrogenation of CO2 into light olefins presents a promising strategy to realize carbon neutrality. Efficient adsorption and activation of CO2 are critical steps in CO2 hydrogenation into light olefins. Nevertheless, the development of a promotional catalyst that obtains high CO2 conversion and C2=-C4= selectivity is challenging, constrained by the chemical inertness of CO2. In this paper, we have synthesized a highly stable catalyst consisting of ZnFe0.38CrOx oxides and SAPO-34 zeolite, which achieves 11.4 % C2=-C4= yield at CO2 conversion up to 35.4 %. Comprehensive characterization results substantiate the existence of electronic interaction among Fe, Zn, and Cr, which facilitates the adsorption and activation of CO2. More significantly, the CO2 adsorption capacity is linearly related to the degree of electron transfer. In situ DRIFTS results further reveal that electronic interaction promotes the production of carbonate species and subsequent transformation into formate species, contributing to high CO2 conversion. These findings uncover an intrinsic connection between electronic interaction and catalytic activity, offering theoretical guidance for designing bifunctional catalysts.

Dataset for carbon dioxide adsorption on lizardite

This paper presents data on the adsorption of CO2 on the (001) and (00 ) surface lizardite. The data were obtained from calculations using the density functional theory (DFT) method implemented in the CASTEP software package. The calculations were performed using the plane wave basis set and the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional. A semi-empirical Grimme D2 correction was used to correctly account for dispersion interactions, which play an important role in physical adsorption processes. The data include optimized geometry and electronic properties of equilibrium states of adsorbed CO2 on (001) and (00 ) lizardite surfaces. They contain the most energetically favorable adsorption sites and estimates of the interaction strength between the adsorbate and adsorbent. The analysis of the electronic structure includes calculations of charge distribution, density of states (DOS), and visualizations of electron density difference isosurfaces. These data provide detailed insights into the redistribution of electron density during adsorption and the nature of the bonds formed. All data, including optimized crystal structures, electronic properties, and calculation results, are available in formats that can be read by commonly available text editors and specialized atomic structure visualization and analysis software. The presented dataset can serve as a foundation for further studies on the interactions of various molecules with the lizardite surface.

Creating CoRu Dual Active Sites Codecorated Stable Porous Ceria Support for Enhanced Li-CO2 Batteries Cathodes.

Lithium-carbon dioxide (Li-CO2) battery represents a high-energy density energy storage with excellent real-time CO2 enrichment and conversion, but its practical utilization is hampered by the development of an excellent catalytic cathode. Here, the synergistic catalytic strategy of designing CoRu bimetallic active sites achieves the electrocatalytic conversion of CO2 and the efficient decomposition of the discharge products, which in turn realizes the smooth operation of the Li-CO2 battery. Moreover, obtained support based on metal-organic frameworks precursors facilitates the convenient diffusion and adsorption of CO2, resulting in higher reaction concentration and lower mass transfer resistance. Meanwhile, the optimization of the interfacial electronic structure and the effective transfer of electrons are achieved by virtue of the strong interaction of CoRu at the support interface. As a result, the Li-CO2 cell assembled based on bimetallic CoRu active sites achieved a discharge capacity of 19,111mAhg-1 and a steady-state discharge voltage of 2.58V as well as a cycle life of >175 cycles at a rate of 100mAg-1. Further experiments combined with density-functional theory calculations achieve a deeply view of the connection between cathode and electrochemical performance and pave a way for the subsequent development of advanced Li-CO2 catalytic cathodes.

Halogen Tailoring of Platinum Electrocatalyst with High CO Tolerance for Methanol Oxidation Reaction.

The catalytic activity of platinum for CO oxidation depends on the interaction of electron donation and back-donation at the platinum center. Here we demonstrate that the platinum bromine nanoparticles with electron-rich properties on bromine bonded with sp-C in graphdiyne (PtBr NPs/Br-GDY), which is formed by bromine ligand and constitutes an electrocatalyst with a high CO-resistant for methanol oxidation reaction (MOR). The catalyst showed peak mass activity for MOR as high as 10.4 A mgPt -1, which is 20.8 times higher than the 20 % Pt/C. The catalyst also showed robust long-term stability with slight current density decay after 100 hours at 35 mA cm-2. Structural characterization, experimental, and theoretical studies show that the electron donation from bromine makes the surface of platinum catalysts highly electron-rich, and can strengthen the adsorption of CO as well as enhance π back-donation of Pt to weaken the C-O bond to facilitate CO electrooxidation and enhance catalytic performance during MOR. The results highlight the importance of electron-rich structure among active sites in Pt-halogen catalysts and provide detailed insights into the new mechanism of CO electrooxidation to overcome CO poisoning at the Pt center on an orbital level.

Synergistic effect of carbon molecular sieve and alkali metal nitrate on promoting intermediate-temperature adsorption of CO2 over MgAl-layered double hydroxide

The development of intermediate-temperature adsorbents with high CO2 adsorption capacity is crucial for the tandem integration with CO2 hydrogenation catalyst, aimed at enhancing economy viability and minimizing energy consumption in Carbon capture, utilization and storage (CCUS). Although certain porous carbon materials (PCM) have been employed to enhance CO2 adsorption capability of layered double hydroxide (LDH), there remains an urgent necessity to identify more cost-effective and efficient PCM alternatives. Herein, alkali metal nitrates ((Li0.3Na0.18K0.52)NO3, hereafter referred to as LiNaK) modified layered double hydroxide (LDH)/carbon molecular sieve (CMS) composite (LiNaK-LDH/CMS) as promising adsorbents for CO2 capture was reported. The effects of CMS addition and nitrate loading, the calcination and adsorption temperature, as well as the cycling stability were investigated systematically. The results revealed that the CO2 capture capacity of the LiNaK-modified layered double oxide (LDO)/CMS composite (30 mol%LiNaK-LDO/CMS15%)-incorporating with 15 wt% CMS addition and 30 mol% nitrate loading-achieved a remarkable CO2 adsorption capacity of 1.32 mmol/g at 300 °C due to the synergetic interactions between CMS and nitrate; this represents nearly a sevenfold enhancement compared to initial LDO performance. Moreover, the 30 mol%LiNaK-LDO/CMS15% adsorbent also demonstrated commendable cyclic stability after ten adsorption cycles, retaining over 85 % of its initial adsorption capacity. Based on both obtained adsorption performance and characterization data from the adsorbents, a pre-adsorption enhancing CO2 intermediate-temperature adsorption mechanism over LiNaK-LDH/CMS composite through air calcination processes. This study significantly advances LDH-based adsorbent for future research into CO2 intermediate-temperature adsorption.

Facile synthesis and biomimetic amine-functionalization of chitosan foam for CO2 capture

A high-performance biomass-based adsorption materials could be the promising trend for CO2 capture and storage technology. However, the direct application of biomass-based porous materials as a CO2 adsorbent with enhanced performance is an emerging issue. Herein, a facile synthesis and a biomimetic strategy were combined to prepare amine-functionalized chitosan foam for CO2 capture, and then a porous biomass is achieved for the application on the environment protection field. Firstly, the chitosan foam was synthesized by the emulsion-templating method at room temperature. Depended on stabilizing n-octane in the chitosan hydrogel with Span 80, a tunable three-dimensional network porous structure was obtained. Subsequently, co-deposition with dopamine (DA) and polyethyleneimine (PEI) was applied to load abundant amine content on the surface of chitosan foam and thereby improving CO2 adsorption capacity. Finally, the as-prepared amine-functionalized chitosan foam exhibited the impressive adsorption capacity of 3.59 mmol/g at 333 K and atmospheric pressure, and the better adsorption selectivity and stability. The results extend the preparation approach of biomass porous materials, and also its application in CO2 adsorption technology.

Amine-impregnated elastic carbon nanofiber aerogel templated by bacterial cellulose for CO2 adsorption and separation

Carbon aerogel has become a promising electrode material for CO2 capture and capacitor due to its large specific surface area, well-developed pore structure, adjustable porosity and ultra-high specific power. However, most of the carbon-based materials suffer from poor mechanical properties, low recycling efficiency, and low adsorption capacity, making it difficult to be put into industrial applications on a large scale. Bacterial cellulose (BC) has an ultra-fine reticular structure, a modulus of elasticity that is several to more than ten times that of typical plant fibers, and high tensile strength. In this paper, BC was treated by unidirectional freeze-drying method, and the aerogels with ordered honeycomb pore structure were constructed by unidirectional growth of ice crystals, and the pyrolytic chemical properties of BC were adjusted by using (NH4)2SO4, which effectively prevented the shrinkage and deformation of materials during carbonization, and successfully prepared elastic nanocarbon fiber aerogels. At the same time, the introduction of (NH4)2SO4 made the material realize N doping in the carbonization process, providing more adsorption sites, which was conducive to the adsorption of CO2. Finally, the carbon fiber nanoaerogel was modified by TEPA to further improve its adsorption selectivity for CO2. The prepared elastic carbon nanofiber aerogel (CBCNT) has high CO2 adsorption performance and high selectivity, and its CO2 capture capacity is up to 4.88 mmol/g. At the same time, its capacitance also reached 246F/g.

Crystal plane engineering-tailored Co-Ni bimetallic sites in CoNiO2 to achieve efficient photocatalytic CO2 reduction

Aligning the atomic structure of catalyst by the crystal-plane engineering is an effective strategy to enhance the photocatalytic activity. In this paper, the CoNiO2 nanosheets (NSs) with (200) and nanorods (NRs) with (111) crystal planes were successfully prepared through a simple hydrothermal method for CO2 photoreduction. The experimental results indicated that the CNO NRs had excellent CO2 photoreduction performance. The CO and CH4 yields over CNO NRs were about 48.66 and 5.84 μmol·g-1·h-1, which were about 2.62 and 2.61 times stronger than that of CNO NSs. Moreover, it was also about 10.70 and 6.25 times as good as the TiO2 commercial powder, respectively. Experimental and theoretical calculations demonstrated that the Co-Ni bimetallic sites on the (111) crystal plane of CNO NRs can effectively enhance the CO2 adsorption and activation ability compared with the single Ni site on the (200) crystal plane of CNO NSs. Besides, the energy barrier required for the development of the critical intermediate *COOH from *CO2 was greatly reduced on the Co-Ni bimetallic sites, thereby improving the CO2 photoreduction activity. The reaction paths were inferred by in-situ FTIR and 13C isotope tracer techniques, and finally a potential enhancement mechanism of the crystal plane engineering induces bimetallic sites to promote CO2 adsorption and activation process has been proposed.

Mechanism of methanol synthesis from CO2 hydrogenation over Rh16/In2O3 catalysts: A combined study on density functional theory and microkinetic modeling

In this study, the hydrogenation of carbon dioxide (CO2) to methanol (CH3OH) over Rh16/In2O3 catalyst was studied through Density Functional Theory (DFT) and microdynamics modeling. The spontaneous dissociation mechanisms of H2 and CO2 adsorption at the Rh16/In2O3 interface were investigated. The oxygen vacancies in In2O3 enhanced the adsorption process. Bader charge analysis revealed a marginal positive charge on Rh16, elucidating the critical insights into the electronic characteristics and catalytic activity. The study established the RWGS+CO-Hydro pathway as the predominant mechanism for methanol synthesis, characterized by a sequential transformation of intermediates: CO2*→COOH*→CO*+OH*→HCO*→CH2O*→CH2OH*→CH3OH*. Furthermore, Degree of Reaction Rate Control (DRC) analysis conducted in the range of 373–873 K and 10–2 to 103 bar identified two principal kinetic phenomena: at lower temperature and higher pressure, the conversion of CO* + H* to HCO* significantly impacted the overall reaction rate. Conversely, at higher temperature, the step from CH2O* + H* to CH3O* was dominate.

Defect-controlled confined growth of nano-MOFs to prepare materials with hierarchical micro/mesoporous structures for efficient CO2 capture

In recent years, nanoporous materials with special structure have been widely used in various fields. In view of the poor stability of MOFs materials and the poor mass transfer ability, in this study, we developed a simple method to restrict the growth of UiO-66-NH2 crystals in hollow silica by “vacuum evaporation” strategy, different kinds of acid regulators were introduced, to obtain a composite material with hierarchical pore structure. By characterizing the physical chemistry and microstructure of the composite adsorbent, and calculating the structural defects under different acid regulation, the adsorption and desorption performance and stability of the adsorbent for CO2 were comprehensively investigated. The mechanism of action on CO2 was further analyzed by in-situ infrared and other techniques. The results show that the change of coordination environment and coordination rate caused by the competition of organic acids, which increases the defects and reduces the nucleation and aggregation effect of UiO-66-NH2, promotes the formation of hierarchical pore structure of the composites. Among them, benzoic acid is the best regulating monocarboxylic acid, which makes UiO-66-NH2 have good dispersion in the cavity and suitable crystal size. The specific surface area of the composite material is 717.96 m2·g-1. At the same time, due to its excellent CO2 adsorption capacity (3.35mmol·g-1) at 298K and 1.06bar, it is 48.07% higher than the original UiO-66-NH2. In order to accomplish the goal of effective CO2 adsorption performance of composites, this study offers a novel approach for the synthesis and modification of MOFs-based composites.

Mechanistic investigations into the removal of Hg0 over Pt-based sorbents by warm syngas cleanup

Commercial sorbents for Hg0 removal from syngas operate at low temperatures (<120 ºC), which impacts the thermal efficiency of integrated gasification and chemical production processes. For the first time, supported Pt-based sorbents with different supports, viz., Pt/SBA-15, Pt/S-40, Pt/ZrO2, Pt/CeO2, and Pt/TiO2 are synthesized for high-temperature (≥200 ºC) Hg0 removal. Pt/SBA-15 shows the highest cumulative Hg0 removal efficiency (>99%) at 270 ºC in N2, which is retained for much higher durations (>20h) compared to the best-reported Pd-based and metal oxide sorbents. Besides amalgam formation, Hg0 removal on Pt/ZrO2 and Pt/CeO2 occurs via oxidation at high temperatures (> 270 ºC), which explains the reduced negative effect of high temperature over these sorbents. In contrast to other supports, the removal efficiency over Pt/SBA-15 is above 99% even in the presence of H2, H2O, and CO2, and is attributed to the hydrophobic mesoporous silica support. DRIFTS studies indicate CO adsorption on the active Pt sites over all sorbents. Based on the inferences obtained, a kinetic model is developed and integrated into a reactor-scale model which effectively simulates the spatio-temporal features of Hg0 sorption over Pt/SBA-15.

Revealing the mechanism of bifunctional PtLa electrocatalyst for highly efficient methanol oxidation, hydrogen evolution, and coupling reaction

The development of clean energy solutions, such as fuel cells and hydrogen energy, is crucial for addressing the global energy shortage. Platinum (Pt)-based catalysts are widely used in fuel cells and hydrogen energy generation (for example, via water electrolysis). However, reducing the amount of Pt used while maintaining the catalytic performance of such catalysts is essential. Herein, PtLa catalysts (PtxLay/C) doped with rare earth element lanthanum (La) with different Pt/La atomic ratios were synthesized using a simple chemical reduction method, resulting in Pt65La35/C, Pt78La22/C, Pt97La3/C, and Pt100/C. These PtxLay/C catalysts exhibited excellent electrocatalytic activity and stability in methanol oxidation reaction (MOR), hydrogen evolution reaction (HER), and their coupling reaction as MOR||HER under alkaline conditions. The mechanism by which La doping enhances the electrocatalytic properties and stability of Pt-based catalysts was investigated using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), aberration-corrected scanning transmission electron microscopy (AC-STEM), in-situ Fourier transform infrared (FTIR) and operando Raman spectroscopy. For HER, La doping facilitated the adsorption and activation of H2O at Pt sites, improving water dissociation and *OH desorption and reducing Pt poisoning by *OH. This enhances both the catalytic performance and stability of PtxLay/C for HER. Pt78La22/C exhibited a considerably lower overpotential of only 111 mV at 100 mA cm−2 compared to commercial 20 wt% Pt/C (Pt/C-Johnson Matthey (JM)), which requires 153 mV. For MOR, La promotes CO bond cleavage and reduces CO adsorption at the Pt sites, thereby enhancing both the performance and stability of the catalysts. The mass activity (MA) of Pt78La22/C for MOR is 4.44 A mg−1Pt, which is 12.33 times higher than that of Pt/C-JM (0.36 A/mgPt), and surpasses those of Pt65La35/C, Pt97La3/C, and Pt100/C (2.93, 0.24, and 2.91 A mg−1Pt, respectively). Additionally, Pt78La22/C exhibited outstanding catalytic performance for MOR||HER, with a current density of 20 mA cm−2 at 1.030 V, demonstrating good stability with negligible voltage changes after a 15 h chronoamperometry (CA) testing. This study provides a new strategy for synthesizing Pt-based catalysts with enhanced efficiency and low-energy input for HER||MOR.

Enhancing adsorbent performance for direct air capture of CO2 by in-situ amine-grafting of layered double hydroxides

The development of efficient and cost-effective CO2 adsorbents is crucial for carbon capture from ultradilute conditions. Amine-grafted mesoporous materials prepared by silane chemical reactions are well-known CO2 adsorbents with high thermal stabilities, but their capacities for direct air capture (DAC) are usually restricted by low amine loadings and CO2 capture capacity. Herein, we present an in-situ amine grafting method that enables high amine loadings by in-situ grafting initial ultrathin LDHs nanosheets in an organic solvent. For in-situ triamine grafted Mg2Al-CO3 LDH (IN-TRI-LDH) amine loading is boosted to 5.91mmol N g−1 and ultimately achieving a remarkable adsorption capacity of 0.98 mmol g−1 at 25°C and 400 ppm CO2, nearly double that of the amine-LDHs grafted through a conventional two-step process. A further 22 % enhancement of the CO2 capacity is observed under 20 RH%. In addition, IN-TRI-LDH maintains a working capacity of 0.85 mmol g−1 at a low desorption temperature of 70 °C. A 50 adsorption–desorption cyclic test under simulated humid DAC conditions shows minimal performance degradation. Such a sufficient working capacity and low desorption temperature reduces the thermal energy consumption to 2.27 GJ t−1 at a desorption temperature of 40 °C.

Cobalt-doped Ni-based catalysts for low-temperature CO2 methanation

The study of the process and mechanism of CO2 activation and the development of low-temperature, high-activity and selective catalysts for CO2 methanation are current research hotspots. In this paper, a series of Ni/Al2O3 catalysts with different Co contents were prepared by using layered double hydroxides (LDHs) as precursors for low-temperature CO2 methanation, and the incorporation of Co promoted the electron transfer from Ni to Co, which facilitated the adsorption and activation of CO2 and H2. The spent catalyst still maintained the layered structure with no significant change in the metal particle size, indicating that the addition of Co significantly improved the long-term stability of the catalysts. The CO2 conversion was 55.5 % and STYCH4 was 148.0 mmol·gcat−1 h−1 at 200 °C, 2.0 MPa and 1000 h−1. The in situ DRIFTS experiments showed that the addition of Co accelerated the conversion of the reaction intermediates and promoted the generation of methane.

Optimal design of PdAu/In2O3 catalysts for CO2 hydrogenation

Efficient catalyst design has garnered significant interest in recent decades due to its potential to address both the challenges of the greenhouse effect and energy shortages by facilitating the conversion of CO2 into valuable chemicals through catalytic reactions. To investigate maximizing the synergistic effects of supported PdAu catalysts, we conducted first-principles calculations on the activation and decomposition of CO2 and H2 on the PdAu/In2O3(110) system. The results demonstrate that the incorporation of a secondary metal (Au) into the supported Pd catalyst, in conjunction with precise control over Au concentration, exerts influence on both reactant binding energy and activation. The adsorption and activation of CO2 at the interface sites of Au4/In2O3(110) and PdAu3/In2O3(110) are not observed. The transition state for the dissociation of CO2 into *CO and *O is determined based on adsorbed CO2, providing insights into the properties of activated CO2. The Bronsted–Evans–Polanyi relation, which correlates activation barriers (Ea) with reaction energies (Er), was established for the CO2 dissociation mechanism on PdAu/In2O3(110) catalysts using equation E = 0.4Ea + 0.63. It was carried out to investigate the H2-dissociated adsorption processes and mobility energy on various PdAu/In2O3(110) catalysts. Finally, a highly efficient Pd2Au2/In2O3 catalyst for the hydrogenation of CO2 into methanol has been proposed. This research provides valuable insights into the hydrogenation of CO2 to methanol using bimetal-oxide catalysts and contributes to the optimization of the design of PdAu/In2O3 catalysts for CO2 reactions.

Interface engineering on single-atom Cu-modified BiOBr1−xClx for efficient artificial photosynthesis of methanol

Converting CO2 into value-added fuels was an attractive way to alleviate the energy crisis. Cu-based catalysts were recognized as the most effective candidates for catalyzing CO2 to solar fuels due to their specific electronic structure. However, selective production of desired fuels from photocatalytic CO2 reduction remained a grand challenge. Herein, the interface engineering of single-atom Cu with BiOBr1−xClx nanosheets (Cu-SA/BOBC) was demonstrated to address this challenge. The single-atom Cu in BOBC favored charge transition, carrier separation, and photon utilization, with a superior performance of CO2 photoreduction yielding CH3OH of 8.21 μmol·g−1·h−1, 94.3 % electron-based CH3OH selectivity. Meanwhile, it could lower the CO2 activation energy barrier, and be conducive to strong CO* adsorption and subsequent hydrogenation of CO* to CHO*, which was critical for the high selectivity of CH3OH. This work highlighted a new insight into regulating the photoreduction of CO2 to CH3OH by interfacial interaction.

Pd-Adsorbing CrS2 monolayer as sensing material for detecting CO, C2H2, and C2H4 in dissolved gases: A first-principles study

This study employs density functional theory to initially examine the adsorption characteristics of Pd atom on CrS2 monolayer (termed Pd@CrS2). Subsequently, the adsorption capabilities of Pd@CrS2 monolayer for CO, C2H2, and C2H4 are simulated to assess its prospects for dissolved gas detection. Stable adsorption of Pd atoms onto the CrS2 monolayer atop Cr atoms is observed with a binding energy of −2.69 eV. Pd@CrS2 exhibits chemisorption towards CO, C2H2, and C2H4 with respective adsorption energies of −1.49, −1.13, and −1.22 eV. The band structure and density of states analysis indicate significant alterations in the electronic properties of CrS2 upon Pd adsorption and upon exposure to the gases. The bandgap of Pd@CrS2 is modified by −29.6 %, −24.7 %, and −27.1 % after CO, C2H2, and C2H4 adsorption, corresponding to highly sensitive detection responses of −99.6 %, −98.9 %, and −99.3 %. The research highlights the gas sensing capabilities of Pd@CrS2 monolayers for monitoring the operational status in dissolved gas analysis, showcasing the promising application potential of CrS2.