Metal Doping Research Articles

Modulating Built‐In Electronic Configuration via Variable Al Doping for Robust Oxygen Evolution Reaction

Transition metal‐based electrocatalysts play a crucial role in the oxygen evolution reaction (OER). However, their heavy reliance on free electrons at the <i>d</i>‐band significantly limits the screening of potentially efficient, earth‐abundant alternatives. Despite extensive exploration of catalyst engineering through multi‐metal cooperation to modulate electron configuration by introducing additional transition metals, practical success remains elusive. Here, we present a straightforward electrodeposition method for preparing amorphous FeCoAl hydroxide catalysts. The introduction of Al contributes external free electrons, enabling a well‐defined electron configuration for intermediate adsorption. Al doping also adjusts the <i>d</i>‐band position of adjacent Co atoms, bringing them closer to the Fermi level and significantly enhancing intrinsic activity at the active sites. Furthermore, Al dopants facilitate rapid mass and charge transfer near the catalyst layer, promoting faster reaction kinetics. Leveraging these properties, the FeCoAl hydroxide catalyst achieves a large current density of 100 mA cm <sup>‐2</sup> at an overpotential of 340 mV, with a small Tafel slope of 29.1 mV dec <sup>‐1</sup>. Our work provides valuable insights for designing efficient electrocatalysts by leveraging free electron‐rich metal doping and expanding the parameter space for catalyst engineering.

Effect of Molybdenum Concentration and Deposition Temperature on the Structure and Tribological Properties of the Diamond-like Carbon Films

Two series of non-hydrogenated diamond-like carbon (DLC) films and molybdenum doped diamond-like carbon (Mo-DLC) films were grown on the silicon substrate using direct current magnetron sputtering. The influence of molybdenum doping (between 6.3 and 11.9 at.% of Mo), as well as the deposited temperature (between 185 and 235 °C) on the surface morphology, elemental composition, bonding microstructure, friction force, and nanohardness of the films, were characterized by atomic force microscopy (AFM), energy dispersive X-ray spectroscopy (EDX), Raman spectroscopy, and a nanoindenter. It was found that the increase in the metal dopant concentration led to a higher metallicity and graphitization of the DLC films. The surface roughness and sp3/sp2 ratio were obtained as a function of the Mo concentration and formation temperature. The nanohardness of DLC films was improved by up to 75% with the addition of Mo. Meanwhile, the reduction in the deposition temperature decreased the nanohardness of the DLC films. The friction coefficient of the DLC films was slightly reduced with addition of the molybdenum.

Hydrodeoxygenation of Isoeugenol-Derived Model Compound over Carbon-Supported Pt and Pt-SnS Catalysts for the Production of Sustainable Jet Fuel.

This study focuses on the sustainable production of bio-jet fuel through the catalytic hydrodeoxygenation (HDO) of isoeugenol (IE). Sucrose-based activated carbon supported bimetallic Platinum-Tin metal sulphides (PtO-SnS/AC) catalyst was prepared for HDO process. Physicochemical properties of catalysts with different spraying synthesis methods (in situ and ex situ metal doping) and Pt loading (0.1-1.0 %) were further investigated. The PtO-SnS/AC catalysts were characterised using various techniques such as X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), field-emission scanning electron microscopy (FESEM) and thermogravimetric analysis (TGA). Both HRTEM and FESEM results show the successful preparation of a spherical nanoparticles doped over activated carbon, and Pt was dispersed on the outer shell of the particles. The catalytic HDO of IE was evaluated in a batch system and showed a high yield and conversion as follows: IE conversion of 100 %, liquid-phase mass balance of 95.92 %, dihydroeugenol (DH) conversion of 99.32 %, propylcyclohexane (PCH) yield of 88.94 % and 2-methoxy-4-propylcyclohexanol (HYD) yield of 76.19 %. Moreover, the PtO-SnS/AC catalyst exhibited high reusability with low metal leaching and high coke resistance for 10 cycles. The catalyst was evaluated in a continuous flow reactor for 100 h at different reaction temperatures, and interestingly, the catalyst showed low deactivation with a high half-time.

Constructing frustrated Lewis pairs on Mo-doped Fe2O3 catalyst to enhance oxidative desulfurization efficiency

The emission of sulfur oxides will not only cause a series of environmental pollution but also threaten human health. At present, oxidative desulfurization is considered one of the technologies to achieve high-efficiency conversion of sulfur-containing compounds. Herein, the special frustrated Lewis pairs (FLPs) for efficient oxidative desulfurization are created by regulating surface doping in a redox iron-based oxide. According to experimental results, the Lewis acidic sites can be considered as the iron atoms adjacent to the molybdenum dopant, while the doped metal proximal to the oxygen vacancies serves as Lewis basic sites to create FLPs in redox iron-based oxide. This reactivity of FLPs is further adapted to the chemical activation of molecular oxygen and aromatic sulfur-containing compounds. The Fe2O3-FLP catalyst can achieve 100 % sulfur removal at 3 h and maintains 96.9 % after seven cycles, higher than other previously reported iron-based oxidative desulfurization catalysts. In addition, the design of FLPs offers a promising approach for developing high-efficiency catalysts in the oxidative desulfurization process.

Mo‐Doped Perovskite Cathode Enables High‐Performance Cycling‐Stable Zinc‐Ion Batteries

AbstractManganese compounds have emerged as promising cathode materials for aqueous zinc‐ion batteries (AZIBs). But their broader applications are impeded by such cathodes' poor structure stability and sluggish ion transportation. Herein, these limitations are addressed by proposing high‐valence Mo doping regnant LaMnO3 perovskite oxide cathodes to develop high‐performance rate stable AZIBs. The optimized doped cathode contributes a highest specific capacity of 445 mAh g−1 at the current density of 0.5 A g−1, which maintains 206 mAh g−1 at 2 A g−1 and accompanies with a remarkable capacity retention of 114% beyond 1000 cycles for continuous charge/discharge process. The doping of multivalent Mo is revealed to boost the energy storage capacity and stabilize the electrode structure via various ex situ characterization and theoretical calculations. Importantly, the incorporation of Mo facilitates the acceleration of reaction kinetics and sufficient charge transfer with H+ and Zn2+ as dual charge carriers, where H+ plays a dominant role. This work provides a new perspective on developing innovative perovskite oxide cathodes with high‐valence metal doping for AZIBs.

Transition Metal-Doped Layered Iron Vanadate (FeV3-xMxO9.2.6H2O, M = Co, Mn, Ni, and Zn) for Enhanced Energy Storage Properties

With its distinctive multiple electrochemical reaction, iron vanadate (FeV3O9.2.6H2O) is considered as a promising electrode material for energy storage. However, it has a relatively low practical specific capacitance. Therefore, using the low temperature sol–gel synthesis process, transition metal doping was used to enhance the electrochemical performance of layered structured FeV3O9.2.6H2O (FVO). According to this study, FVO doped with transition metals with larger interlayer spacing exhibited superior electrochemical performance than undoped FVO. The Mn-doped FVO electrode showed the highest specific capacitance and retention of 143 Fg−1 and 87%, respectively, while the undoped FVO showed 78 Fg−1 and 54%.

Alkali and alkaline earth metals induced n-type surface transfer doping of diamond: A first-principles calculation

The advancement of diamond-based electronic devices is hindered by the n-type doping in diamond, which is a major challenge for diamond. Surface transfer doping is an effective way for modulating the surface conductivity. In this study, we propose and select eight kinds of alkali and alkaline earth metals with low electronegativities as n-type surface dopants on F-terminated diamond using first-principles calculations. Our results reveal n-type doping is realized on diamond surface, and a negative correlation between the electronegativity of metal dopants and areal electron density. High areal electron densities of 2.975 × 1013 and 3.102 × 1013cm-2 and room-temperature electron mobilities of 1102 and 1152 cm2 V-1 s-1 are obtained on Rb and Cs doped diamond surfaces, respectively. Our findings provide a way for designing of n-type diamond, and it is helpful for the understanding of the surface doping mechanism for semiconductors.

A review of doped metal oxide semiconductors in the stability of thin film transistors

A review of doped metal oxide semiconductors in the stability of thin film transistors

A general flame aerosol route to kinetically stabilized metal-organic frameworks

Metal-organic frameworks (MOFs) are highly attractive porous materials with applications spanning the fields of chemistry, physics, biology, and engineering. Their exceptional porosity and structural flexibility have led to widespread use in catalysis, separation, biomedicine, and electrochemistry. Currently, most MOFs are synthesized under equilibrium liquid-phase reaction conditions. Here we show a general and versatile non-equilibrium flame aerosol synthesis of MOFs, in which rapid kinetics of MOF formation yields two distinct classes of MOFs, nano-crystalline MOFs and amorphous MOFs. A key advantage of this far-from-equilibrium synthesis is integration of different metal cations within a single MOF phase, even when this is thermodynamically unfavorable. This can, for example, produce single-atom catalysts and bimetallic MOFs of arbitrary metal pairs. Moreover, we demonstrate that dopant metals (e.g., Pt, Pd) can be exsolved from the MOF framework by reduction, forming nanoclusters anchored on the MOF. A prototypical example of such a material exhibited outstanding performance as a CO oxidation catalyst. This general synthesis route opens new opportunities in MOF design and applications across diverse fields and is inherently scalable for continuous production at industrial scales.

Transition metal doping for tailoring magnetic properties of graphdiyne

Tailoring the magnetic properties of semiconductors is crucial for realizing spintronic devices with integrated logic and memory functions. Graphdiyne (GDY), a two-dimensional carbon semiconductor, has emerged as a promising material for this purpose. This work demonstrates an effective approach to induce robust room-temperature ferromagnetism in GDY through in-situ transition metal (Fe, Co, Ni) doping via an improved liquid-liquid interface synthesis method. Density functional theory calculations reveal that the ferromagnetism originates from the Kagome lattice formed by the doped transition metal atoms. Remarkably, Fe-doped GDY exhibits a saturation magnetization of 2.86 emu · g−1 at room temperature, substantially higher than Co- and Ni-doped counterparts. Furthermore, post synthesis annealing treatment allows modulating the magnetic properties by introducing hydroxyl groups, with Co-GDY annealed at 500°C showing optimal room-temperature ferromagnetic behavior (0.26 emu · g−1). This work paves the way for tailoring magnetic semiconductors for spintronic applications by leveraging transition metal doping and defect engineering in graphdiyne.

One-pot synthesis of transition metals-doped LiAl-LDHs to improve lithium adsorption performance and stability

Transition metal doping of Li/Al-LDHs can alter the interlayer spacing and surface charge of LDHs, thereby enhancing adsorption performance and stability. To investigate the rules and mechanisms governing the enhancement of stability and adsorption capacity of Li/Al-LDHs through transition metal element doping, several transition metal elements (Co, Zn, Mn, Zr, and Ni) were selected, and the five types of transition metal-doped Li/Al-LDHs and one undoped Li/Al-LDHs were synthesized by a one-pot method. Compared to the original Li/Al-LDHs, the Co-doped Li/Al-LDHs exhibited higher adsorption capacity, lower dissolution loss, and greater stability. Additionally, after Co doping, the lattice constant of Li/Al-LDHs decreases, effectively reducing the intercalation energy and increasing lithium diffusion efficiency. When used for lithium adsorption, Co-Li/Al-LDHs exhibited a Li+ capacity of 12.6 mg/g and reached saturation adsorption within 90 min. Notably, Co-Li/Al-LDHs achieved a high Li+ adsorption capacity (6.46 mg/g) in East Taigener salt-lake brine. After 10 cycles, the adsorption capacity did not show any significant change, and after 336 h adsorption-desorption cycles (200 rmp, oscillation), the total Al dissolution loss was only about 0.035 ‰, demonstrating that Co doping can enhance the interlayer binding force of Li/Al-LDHs, thereby reducing the decomposition of the layered structure in solution, lowering aluminum dissolution loss, and improving structural stability. The results show that doping with transition metals can reduce the Al dissolution rate of LDHs, and Co-Li/Al-LDHs can be used as an efficient adsorbent for lithium extraction from salt lake and have higher stability.

Producing aromatic‐rich oil through microwave‐assisted catalytic pyrolysis of low‐density polyethylene over Ni/Co/Cu‐doped Ga/ZSM‐5 catalysts

AbstractMicrowave (MW)‐assisted catalytic pyrolysis represents a promising method for transforming petroleum‐based plastic waste into valuable chemicals, offering a pathway towards more sustainable circular economy. In this study, catalytic pyrolysis of low‐density polyethylene (LDPE) was conducted under MW irradiation. The influence of various catalyst types (HZSM‐5, Ga/ZSM‐5, Ga/Ni/ZSM‐5, Ga/Co/ZSM‐5, and Ga/Cu/ZSM‐5) on product yield and distribution was examined. The results revealed that the Ga/ZSM‐5 catalyst yielded the maximum liquid oil, approximately 41%. Ga/Ni/ZSM‐5 performed excellently in the production of long‐chain olefins, constituting about 27% of the liquid fraction. However, Ga/Co/ZSM‐5 led to the production of heavy pyrolysis oil containing nearly 25% long‐chain paraffins, rendering it unsuitable for producing high‐value chemicals. Conversely, the Ga/Cu/ZSM‐5 catalyst yielded an aromatic‐rich pyrolysis oil, with benzene derivatives constituting approximately 90% of the liquid oil fraction, thus proving to be a suitable catalyst for the intended application. The liquid product distribution was compared with a petroleum assay by SimDist, and this suggested that utilizing the HZSM‐5 catalyst could yield an 86.4% naphtha fraction. The study also revealed that the Ga/Cu/ZSM‐5 catalyst generated the largest amounts of hydrogen and syngas, as determined by a MicroGC analysis of the gas products. This catalyst also exhibited the maximum coke deposition (1.35%) postreaction, which was attributed to its high aromatic hydrocarbon content in the pyrolysis oil and maximal hydrogen release. A comparison of fresh and spent catalyst properties was conducted to gain insights into catalyst activity and to correlate the effects of metal doping on product distribution. These findings underscore the potential of MW‐assisted catalytic pyrolysis, particularly with the Ga/Cu/ZSM‐5 catalyst, for the efficient conversion of plastic waste into valuable chemicals, thereby contributing to sustainable resource utilization and environmental conservation.

Metals doping effect of perovskite–type La-Mn oxides for NH3-SCR reaction at low temperature

Doping of perovskites with the heteroatoms has emerged as an additional lever, a dimension beyond structural perfection and compositional distinction, for the alteration of many properties of perovskites. In this work, a series of different metals were doped via citric acid sol–gel method to investigate their influences on the structure and catalytic performance of La-Mn perovskite oxides for NH3-SCR reaction. It is found that Zr doped La-Mn oxides (LMZr) displays better low-temperature deNOx performance (T90 = 118 °C) than other metal doped catalysts. Such a result is mainly attributed to the increase of Lewis acid sites, surface Mn4+ and adsorbed oxygen species. Besides, La-Mn perovskite doped with Sr, Ce, Y and Al can also obviously improve low-temperature deNOx activity and N2 selectivity. These doped metals mainly change the electron transfer between different cations, thus changing the valence distribution of Mn on the surface, meanwhile, metal doping changes the crystalline size of the catalysts, thereby affecting the adsorption and activation of NH3 and O2 involved in the removal of NO. Although other metal doping alters the tolerance of the La-Mn catalyst to SO2 and/or H2O, SO2 is inevitably oxidized to S6+ and deposits on the catalyst surface. Zr or Ce doping significantly enhances the tolerance to SO2 and/or H2O, but they have a different mechanism. Zr reduces the deposition rate of sulfate while Ce reacts with SO2 to form Ce2(SOx)3 to protect Mn active species. This paper highlights the importance of Lewis acid, Mn4+ content and adsorbed oxygen in the NH3-SCR reaction.

Unlocking the potential of eggplant peel: Powerful peroxidase nanozyme for l-cysteine determination in pharmaceutical supplements

For the first time, eggplant peel biowaste was upcycled through a very fast one-pot microwave synthesis to produce cost-effective and environmentally friendly blue-fluorescent carbon dots (EPE-CDs). The resulting EPE-CDs emitted fluorescence at 465 nm when excited at 400 nm and exhibited enhanced peroxidase-like behavior without metal doping requirement. They were able to oxidize o-phenylenediamine (OPD) in the presence of hydrogen peroxide (H2O2) to generate 2,3-diaminophenazine (DAP) leading to a new emission peak at 560 nm. Through the inner filter effect, DAP was able to quench the fluorescence of EPE-CDs, causing a change from colourless to yellow. By leveraging the fluorescence characteristics of EPE-CDs and DAP, dual-emission platform was established. This platform could be used for the catalytic detection of H2O2 within the 10–110 μM range. The introduction of L-Cysteine, containing reductive thiols that hinder DAP production, resulted in a reduction in the fluorescence intensity of DAP. The study demonstrated that fluorescence intensities ratio 465 nm / 560 nm (I465/I560) exhibited a linear relationship with L-Cysteine concentration between 4 and 60 μM, reaching detection limit as low as 0.69 μM. Furthermore, when applying the ratiometric fluorescence platform to quantify L-Cysteine in actual samples, the average recoveries ranged from 99.50 % to 101.40 %, with a relative standard deviation (RSD) not exceeding 2 %. Through the exploration of the fluorescence properties and nanozyme-like capabilities, this research offers a novel perspective on utilizing biowaste sources for CD synthesis and utilization of these CDs as nanozymes.

Mechanism of Sulfate Radical Formation on Activation of Persulfate Using Doped Metal Oxide and Its Role in Degradation of Tartrazine Dye in an Aqueous Solution.

Degradation of tartrazine dye (TZD) was performed in this study using sulfate radicals (SO4•-) generated from the activated sodium persulfate (SPS) using Fe3O4@PDA nanoparticles (NPs). The NPs were characterized by Fourier transform infrared (FTIR), vibrating sample magnetometer (VSM), X-ray diffraction (XRD), high-resolution scanning electron microscopy (HR-SEM), X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (HRTEM), and energy-dispersive X-ray spectroscopy (EDX). The average particle size of the NPs was 17.49 nm from XRD analysis. The presence of the C-N group at 1129 cm-1 in FTIR and 2.54% of the nitrogen element identified from the EDX plot was evidence of successful doping of polydopamine (PDA). Superparamagnetic nature with a decrease in the Ms value to 42.015 emu/g after doping was determined. Doping was further confirmed by XPS analysis with binding energies at 399.68 and 400.99 eV. The average particle size from HRTEM analysis was 21.47 nm with a lattice spacing of 0.30 nm. Turnover number (TON) and turnover frequency (TOF) values for Fe3O4@PDA were determined to be 3.72 and 0.0248 min-1 with respect to different systems, respectively. Optimum conditions for the Fe3O4@PDA/SPS system were 50 ppm TZD, 0.9 g/L catalyst, 12 mM SPS, and pH 4 with 94.68% efficiency in 150 min. The inhibition effect of ions in TZD degradation followed the order humic acid <NO3- < Cl- < CO32. The kinetic model fitting the Fe3O4@PDA/SPS system has pseudo-second-order kinetics. Excess formation of SO4•- produced hydroxyl radicals (•OH) that were identified by a scavenging test. Reusability of the NPs was performed for five cycles and showed acceptable degradation performance up to 82.47%. The intermediates identified from gas chromatography-mass spectrometry (GCMS) proved the cleavage of azo and sulfonate groups of TZD with the formation of nontoxic intermediates. Finally, the phytotoxicity assessment was studied using Vigna radiata (Green grams). The % decrease of the root, shoot, and seedling length for the degraded dye solution was negligible. Hence, this study proved that the Fe3O4@PDA/SPS system could effectively degrade TZD with nontoxic intermediate formation.

On the Nature of HOPG-Supported Pt1Ti2O7 and its Decomposition of a Nerve Agent Simulant: A Cluster Model of a Single Atom Catalyst Active Site.

Chemical weapons, including hyper lethal nerve agents, are a persistently looming threat across the modern geopolitical landscape. There is a pressing need for the design and development of improved protective materials, which can be substantially aided by the cultivation of a fundamental molecular-level understanding of candidate systems and the corresponding decomposition chemistry. The emergence of the exciting new class of single atom catalyst (SAC) materials has enhanced the prospect of subnanoscale design tailoring in the hopes of optimizing activity and selectivity for a variety of chemical applications. Here, we apply our recently developed experimental technique for modeling the active sites of such SAC materials through the preparation of surface supported size-selected single metal-atom doped metal oxide clusters. The propensity for an SAC cluster model system for Pt1/TiO2 materials, Pt1Ti2O7 supported on highly oriented pyrolytic graphite (HOPG), to adsorb and decompose nerve agent simulant dimethyl methylphosphonate (DMMP) was investigated through a combination of temperature-programmed desorption/reaction (TPD/R) and X-ray photoelectron spectroscopy (XPS). XPS measurements of the as-prepared Pt1Ti2O7 clusters supported the successful isolation of single Pt atoms in clusters monodispersed across the HOPG surface. TPD/R experiments showed that the reactivity exhibited by the Pt1Ti2O7 clusters was distinct from that of Ti2O7 clusters lacking the single Pt atom. It was found that DMMP decomposed over Pt1Ti2O7 upon heating to as low as room temperature, and higher temperature treatments evolved exclusively H2O, CO, and H2, while decomposition over Ti2O7 evolved only methanol and formaldehyde at elevated temperatures. This indicated the promotion of C-H and PO-C bond cleavage within DMMP due to the presence of single Pt atoms in the clusters. Further, the Pt1Ti2O7 clusters were found to desorb P-containing decomposition species, preventing active site poisoning; however, a change of reactivity reflecting that of Ti2O7 was observed following a single TPD/R cycle. This suggested the encapsulation of active Pt sites by titanium oxide during high temperature treatment and is thus an issue deserving of serious attention in the study of Pt1/Ti2O7 SAC materials.

Electron Arrangement and Transfer Regulation of Li2ZrO3 by Metal Doping for Enhanced CO2 Removal at High Temperatures: A Theoretical and Experimental Study

Electron Arrangement and Transfer Regulation of Li₂ZrO₃ by Metal Doping for Enhanced CO₂ Removal at High Temperatures: A Theoretical and Experimental Study

Development of highly oriented crystals in the magnetoplumbite structure of metal (Sr, Cr, Sc) doped M-type BaFe12O19 hexaferrite films with improved optical and magnetic properties

We have deposited magnetoplumbite (P63/mmc) structured Ba-hexaferrite (BaFe12O19) and its metal (T: Sc and Cr) doped (Ba0.7Sr0.3Fe12O19 and BaFe11.5T0.5O19) films on Si substrate using the Pulsed Laser Deposition technique. The as-grown films showed preferential orientation of the crystals along (2 0 3), (2 0 7), (1 1 14), and (4 0 5) directions. The post-heat treatment oriented the crystals only along (2 0 7) direction. The Fe ions varied it charge state from +3 at the surface of the films to a mixed charge state in the interior, which promoted a local clustering of Fe3O4-like phase. Ferrimagnetic properties of the hexaferrite films have been modified due to metal doping. The bi-phased magnetic structure, arising from clustering of the soft ferrimagnetic Fe3O4 phase in the matrix of hard ferrimagnetic hexaferrite films, is suitable for tuning the magnetic coercivity and moment over a wide range of temperatures. The optical band gap in the range of 3.40–3.50 eV and a strong magneto-optical Kerr signal are promising for potential applications of the films in magneto-optical devices working in UV regime of radiation.

11.88% Efficient Flexible Ag-Free CZTSSe Solar Cell: Spontaneously Tailoring the Alkali Metal Level.

Alkali metal is the requirement for highly efficient Cu2ZnSn(S, Se)4 (CZTSSe) solar cells, thus it is crucial to additionally incorporate alkali metal into the absorber layer for flexible solar cells. However, the efficiency of flexible CZTSSe devices reported to date, based on the conventional alkali incorporation strategies, still lags behind those made on rigid substrates. One of the main issues is the inability to control the alkali content and distribution in the absorber layer. Here, a facile alkaline incorporation approach is proposed, effectively regulating the content and distribution of alkali metals in the film. Such a method can spontaneously tailor the alkali metal content to a proper level, thus leading to the suppression of non-radiative recombination and a better carrier transport through the enhanced film quality and the optimized band binding structure. Finally, a champion flexible CZTSSe solar cell with an efficiency of 11.88% is achieved, the highest reported efficiency for a CZTSSe solar cell without noble Ag doping. This study affords an innovative spontaneous alkali-doping design for the preparation of high-performance flexible CZTSSe solar cells and provides a deeper insight into the extent of alkali metal doping.

Effective Screening of Metal Dopants for In2O3 Catalyst to Tune Catalytic Performance of CO2 Hydrogenation to Formic Acid

The metal doping is an effective strategy to adjust catalytic performance for indium oxide catalyst in CO2 hydrogenation. In current work, a series dopant, Co, Fe, Ni, Pd, Pt, Rh and Ru, are selected and examined in CO2 hydrogenation to formic acid by DFT based microkinetic simulation. It is found that substitutional doping is local effect which mainly promotes the reactivity of adjacent oxygen atoms. The calculations of both CO2 adsorption and hydrogen molecule dissociation certify the positive effects induced by doping, and the adsorption energy of CO2 has a linear relation with the transferred charges for all investigated catalysts which helps to explain the C‐O bond activation mechanism. Two pathways, Formate and Carboxyl, are investigated under same footing. It is noted that doping significantly reduces the hydrogenation barriers on two pathways compared with undoped surfaces. Moreover, the calculated TOF of formic acid formation is greatly increased on doped surfaces and Pt, Pd, Ru are identified as the most active dopants. In the end, it is concluded that reaction obeys Carboxyl mechanism and a valid descriptor of trans‐HCOOH* and H* formation energy is proposed for the screening of effective dopants.