Unconventional hcp/fcc Nickel Heteronanocrystal with Asymmetric Convex Sites Boosts Hydrogen Oxidation.

Developing non-platinum group metal catalysts for the sluggish hydrogen oxidation reaction (HOR) is critical for alkaline fuel cells. To date, Ni-based materials are the most promising candidates but still suffer from insufficient performance. Herein, we report an unconventional hcp/fcc Ni (u-hcp/fcc Ni) heteronanocrystal with multiple epitaxial hcp/fcc heterointerfaces and coherent twin boundaries, generating rugged surfaces with plenty of asymmetric convex sites. Systematic analyses discover that such convex sites enable the adsorption of *H in unusual bridge positions with weakened binding energy, circumventing the over-strong *H adsorption on traditional hollow positions, and simultaneously stabilizing interfacial *H2O. It thus synergistically optimizes the HOR thermodynamic process as well as reduces the kinetic barrier of the rate-determining Volmer step. Consequently, the developed u-hcp/fcc Ni exhibits the top-rank alkaline HOR activity with a mass activity of 40.6 mA mgNi-1 (6.3 times higher than fcc Ni control) together with superior stability and high CO-tolerance. These results provide a paradigm for designing high-performance catalysts by shifting the adsorption state of intermediates through configuring surface sites.

Hybridization State Transition under Working Conditions: Activity Origin of Single-Atom Catalysts.

Single-atom catalysts (SACs) have been widely investigated and have emerged as a transformative approach in electrocatalysis. Despite their clear structure, the origin of their exceptional activity remains elusive. Herein, we elucidate a common phenomenon of the hybridization state transition of metal centers, which is responsible for the activity origin across various SACs for different reactions. Focusing on N-doped carbon-supported Ni SAC (NiN4 SAC) for CO2 reduction reaction (CO2RR), our comprehensive computations successfully clarify the hybridization state transition under working conditions and its relation with the activity. This transition, triggered by the reaction intermediates and applied potential, converts the Ni center from the inert dsp2 hybridization state to the active d2sp3 hybridization state. Importantly, the calculated activity and selectivity of the CO2RR over the d2sp3-hybridized Ni center are consistent with the experimental results, offering strong support for the proposed hypothesis. This work suggests a universal principle of electronic structure evolution in SACs that could revolutionize catalyst design, which also introduces a new paradigm for manipulating electronic states to enhance catalytic performance, with implications for various reactions and catalyst platforms.

Heavily Doped Carbon Nitride Nanocrystal Promotes Visible-Near-Infrared Photosynthesis of Hydrogen Peroxide with Near-Unit Photon Utilization.

Direct photosynthesis of hydrogen peroxide (H2O2) from water and oxygen represents an intriguing alternative to the current indirect process involving the reduction and oxidation of quinones. However, limited light utilization and sluggish charge transfer largely impede overall photocatalytic efficiency. Herein, we present a heavily doped carbon nitride (CNKLi) nanocrystal for efficient and selective photoproduction of H2O2 via a two-electron oxygen reduction reaction (ORR) pathway. CNKLi induces metal-to-ligand charge transfer (MLCT) and electron trapping, which broadens the light absorption to the visible-near-infrared (vis-NIR) spectrum and prolongs the photoelectron lifetime to the microsecond time scale with an exceptional charge diffusion length of ∼1200 nm. Near-unit photoutilization with an apparent quantum yield (AQY) of 100% for H2O2 generation is achieved below 420 nm. Impressively, CNKLi exhibits an appreciable AQY of 16% at 700 nm, which reaches the absorption capacity (∼16%), thus suggesting a near-unit photon utilization <700 nm. In situ characterization and theoretical calculations reveal the facilitated charge transfer from K+ to the heptazine ring skeleton. These findings provide an approach to improve the photosynthetic efficiency of direct H2O2 preparation in the vis-NIR region and expand applications for driving kinetically slow and technologically desirable oxidations or high-value chemical generation.

Computational electrocatalysis beyond conventional hydrogen electrode model: CO2 reduction to C2 species on copper facilitated by dynamically formed solvent halide ions at the solid-liquid interface.

The reduction of CO2 into value-added chemicals and fuels has been actively studied as a promising strategy for mitigating carbon dioxide emissions. However, the dilemma for the experimentalist in choosing an appropriate reaction medium and neglecting the effect of solvent ions when using a simple thermochemical model, normally leads to the disagreement between experimental observations and theoretical calculations. In this work, by considering the effects of both the anion and cation, a more realistic CO2 reduction environment at the solid-liquid interface between copper and solvent ions has been systematically studied by using ab initio molecular dynamics and density functional theory. We revealed that the co-occurrence of alkali ions (K+) and halide ions (F-, Cl-, Br-, and I-) in the electric double layer (EDL) can enhance the adsorption of CO2 by more than 0.45 eV compared to that in pure water, and the calculated energy barrier for CO-CO coupling also decreases 0.32 eV in the presence of I ion on a negatively charged copper electrode. The hydrated ions can modulate the distribution of the charge near the solid-liquid interface, which significantly promotes CO2 reduction and meanwhile impedes the hydrogen evolution reaction. Therefore, our work unveils the significant role of halide ions at the electrode-electrolyte interface for promoting CO2 reduction on copper electrode.

Mechanism of surface oxygen-containing species promoted electrocatalytic CO2 reduction.

Oxygen-containing species have been demonstrated to play a key role in facilitating electrocatalytic CO2 reduction (CO2RR), particularly in enhancing the selectivity towards multi-carbon (C2+) products. However, the underlying promotion mechanism is still under debate, which greatly limits the rational optimization of the catalytic performance of CO2RR. Herein, taking CO2 and O2 co-electrolysis over Cu as the prototype, we successfully clarified how O2 boosts CO2RR from a new perspective by employing comprehensive theoretical simulations. Our results demonstrated that O2 in feed gas can be rapidly reduced into *OH, leading to the partial oxidation of Cu surface under reduction conditions. Surface *OH accelerates the formation of quasi-specifically adsorbed K+ due to the electrostatic interaction between *OH and K+ ions, which significantly increases the concentration of K+ near the Cu surface. These quasi-specifically adsorbed K+ ions can not only lower the C-C coupling barriers but also promote the hydrogenation of CO2 to improve the CO yield rate, which are responsible for the remarkably enhanced efficiency of C2+ products. During the whole process, O2 co-electrolysis plays an indispensable role in stabilizing surface *OH. This mechanism can be also adopted to understand the effect of high pH of electrolyte and residual O in oxide-derived Cu (OD-Cu) on the catalytic efficiency towards C2+ products. Therefore, our work provides new insights into strategies for improving C2+ products on the Cu-based catalysts, i.e., maintaining partial oxidation of surface under reduction conditions.

Cascade Dual Sites Modulate Local CO Coverage and Hydrogen-Binding Strength to Boost CO2 Electroreduction to Ethylene.

Rationally modulating the binding strength of reaction intermediates on surface sites of copper-based catalysts could facilitate C-C coupling to generate multicarbon products in an electrochemical CO2 reduction reaction. Herein, theoretical calculations reveal that cascade Ag-Cu dual sites could synergistically increase local CO coverage and lower the kinetic barrier for CO protonation, leading to enhanced asymmetric C-C coupling to generate C2H4. As a proof of concept, the Cu3N-Ag nanocubes (NCs) with Ag located in partial Cu sites and a Cu3N unit center are successfully synthesized. The Faraday efficiency and partial current density of C2H4 over Cu3N-Ag NCs are 7.8 and 9.0 times those of Cu3N NCs, respectively. In situ spectroscopies combined with theoretical calculations confirm that Ag sites produce CO and Cu sites promote asymmetric C-C coupling to *COCHO, significantly enhancing the generation of C2H4. Our work provides new insights into the cascade catalysis strategy at the atomic scale for boosting CO2 to multicarbon products.

Steering the Selectivity of Carbon Dioxide Electroreduction from Single-Carbon to Multicarbon Products on Metal-Organic Frameworks via Facet Engineering.

Although metal-organic frameworks (MOFs) have attracted more attention for the electrocatalytic CO2 reduction reaction (CO2RR), obtaining multicarbon products with a high Faradaic efficiency (FE) remains challenging, especially under neutral conditions. Here, we report the controlled synthesis of stable Cu(I) 5-mercapto-1-methyltetrazole framework (Cu-MMT) nanostructures with different facets by rationally modulating the reaction solvents. Significantly, Cu-MMT nanostructures with (001) facets are acquired using isopropanol as a solvent, which favor multicarbon production with an FE of 73.75% and a multicarbon:single-carbon ratio of 3.93 for CO2RR in a neutral electrolyte. In sharp contrast, Cu-MMT nanostructures with (100) facets are obtained utilizing water, promoting single-carbon generation with an FE of 63.98% and a multicarbon: single-carbon ratio of only 0.18. Furthermore, this method can be extended to other Cu-MMT nanostructures with different facets in tuning the CO2 reduction selectivity. This work opens up new opportunities for the highly selective and efficient CO2 electroreduction to multicarbon products on MOFs via facet engineering.

Mechanism-Guided Design of Photocatalysts for CO2 Reduction toward Multicarbon Products.

Photocatalytic reduction of CO2 to high value-added multicarbon (C2+) products is an important way to achieve sustainable production of green energy but limited by the low efficiency of catalysts. One fundamental issue lies in the high complexity of catalyst structure and reaction process, making the rational catalyst design and targeted performance optimization a grand challenge. Herein, we performed a mechanism-guided design of photocatalysts for CO2 reduction by using the experimentally reported Cu doped TiO2 (Cu-TiO2) with high C3H8 selectivity and well-defined structure as the prototype. Our mechanistic study highlights three key factors for C3H8 formation, i.e., formation of double O vacancies (Vdi-O) for selectivity, C-C coupling for activity, and Vdi-O recovery for durability. More importantly, Vdi-O formation/recovery and C-C coupling are negatively correlated, indicating that ideal candidates should achieve a balance between oxygen vacancy (VO) formation and C-C coupling. On this basis, TiO2 with the doping of two adjacent Cu atoms (Cu-Cu-TiO2) was designed with enhanced performance for CO2 photoreduction toward C3H8. Furthermore, a simple descriptor (Nµ, "effective d electron number") based on inherent atomic properties was constructed to uncover the underlying causes of the performance variation of different systems. These results provide new insights into the "structure-performance" relation of metal oxide-based photocatalysts, thus offering useful strategies for the rational design of excellent catalysts for CO2 photoreduction.

Phase-dependent growth of Pt on MoS2 for highly efficient H2 evolution.

Crystal phase is a key factor determining the properties, and hence functions, of two-dimensional transition-metal dichalcogenides (TMDs)1,2. The TMD materials, explored for diverse applications3-8, commonly serve as templates for constructing nanomaterials3,9 and supported metal catalysts4,6-8. However, how the TMD crystal phase affects the growth of the secondary material is poorly understood, although relevant, particularly for catalyst development. In the case of Pt nanoparticles on two-dimensional MoS2 nanosheets used as electrocatalysts for the hydrogen evolution reaction7, only about two thirds of Pt nanoparticles were epitaxially grown on the MoS2 template composed of the metallic/semimetallic 1T/1T' phase but with thermodynamically stable and poorly conducting 2H phase mixed in. Here we report the production of MoS2 nanosheets with high phase purity and show that the 2H-phase templates facilitate the epitaxial growth of Pt nanoparticles, whereas the 1T' phase supports single-atomically dispersed Pt (s-Pt) atoms with Pt loading up to 10 wt%. We find that the Pt atoms in this s-Pt/1T'-MoS2 system occupy three distinct sites, with density functional theory calculations indicating for Pt atoms located atop of Mo atoms a hydrogen adsorption free energy of close to zero. This probably contributes to efficient electrocatalytic H2 evolution in acidic media, where we measure for s-Pt/1T'-MoS2 a mass activity of 85 ± 23 A [Formula: see text] at the overpotential of -50 mV and a mass-normalized exchange current density of 127 A [Formula: see text] and we see stable performance in an H-type cell and prototype proton exchange membrane electrolyser operated at room temperature. Although phase stability limitations prevent operation at high temperatures, we anticipate that 1T'-TMDs will also be effective supports for other catalysts targeting other important reactions.

Synthesis of 2H/fcc-Heterophase AuCu Nanostructures for Highly Efficient Electrochemical CO2 Reduction at Industrial Current Densities.

Structural engineering of nanomaterials offers a promising way for developing high-performance catalysts toward catalysis. However, the delicate modulation of thermodynamically unfavorable nanostructures with unconventional phases still remains a challenge. Here, the synthesis of hierarchical AuCu nanostructures is reported with hexagonal close-packed (2H-type)/face-centered cubic (fcc) heterophase, high-index facets, planar defects (e.g., stacking faults, twin boundaries, and grain boundaries), and tunable Cu content. The obtained 2H/fcc Au99 Cu1 hierarchical nanosheets exhibit excellent performance for the electrocatalytic CO2 reduction to produce CO, outperforming the 2H/fcc Au91 Cu9 and fcc Au99 Cu1 . The experimental results, especially those obtained by in-situ differential electrochemical mass spectroscopy and attenuated total reflection Fourier-transform infrared spectroscopy, suggest that the enhanced catalytic performance of 2H/fcc Au99 Cu1 arises from the unconventional 2H/fcc heterophase, high-index facets, planar defects, and appropriate alloying of Cu. Impressively, the 2H/fcc Au99 Cu1 shows CO Faradaic efficiencies of 96.6% and 92.6% at industrial current densities of 300 and 500 mA cm-2 , respectively, as well as good durability, placing it among the best CO2 reduction electrocatalysts for CO production. The atomically structural regulation based on phase engineering of nanomaterials (PEN) provides an avenue for the rational design and preparation of high-performance electrocatalysts for various catalytic applications.

Epitaxial growth of highly symmetrical branched noble metal-semiconductor heterostructures with efficient plasmon-induced hot-electron transfer.

Epitaxial growth is one of the most commonly used strategies to precisely tailor heterostructures with well-defined compositions, morphologies, crystal phases, and interfaces for various applications. However, as epitaxial growth requires a small interfacial lattice mismatch between the components, it remains a challenge for the epitaxial synthesis of heterostructures constructed by materials with large lattice mismatch and/or different chemical bonding, especially the noble metal-semiconductor heterostructures. Here, we develop a noble metal-seeded epitaxial growth strategy to prepare highly symmetrical noble metal-semiconductor branched heterostructures with desired spatial configurations, i.e., twenty CdS (or CdSe) nanorods epitaxially grown on twenty exposed (111) facets of Ag icosahedral nanocrystal, albeit a large lattice mismatch (more than 40%). Importantly, a high quantum yield (QY) of plasmon-induced hot-electron transferred from Ag to CdS was observed in epitaxial Ag-CdS icosapods (18.1%). This work demonstrates that epitaxial growth can be achieved in heterostructures composed of materials with large lattice mismatches. The constructed epitaxial noble metal-semiconductor interfaces could be an ideal platform for investigating the role of interfaces in various physicochemical processes.

Adaptive Design of Alloys for CO2 Activation and Methanation via Reinforcement Learning Monte Carlo Tree Search Algorithm.

Data-driven machine learning (ML) has earned remarkable achievements in accelerating materials design, while it heavily relies on high-quality data acquisition. In this work, we develop an adaptive design framework for searching for optimal materials starting from zero data and with as few DFT calculations as possible. This framework integrates automatic density functional theory (DFT) calculations with an improved Monte Carlo tree search via reinforcement learning algorithm (MCTS-PG). As a successful example, we apply it to rapidly identify the desired alloy catalysts for CO2 activation and methanation within 200 MCTS-PG steps. To this end, seven alloy surfaces with high theoretical activity and selectivity for CO2 methanation are screened out and further validated by comprehensive free energy calculations. Our adaptive design framework enables the fast computational exploration of materials with desired properties via minimal DFT calculations.

A simple descriptor for the nitrogen reduction reaction over single atom catalysts.

The performance of supported catalysts is largely decided by metal-support interactions, which is of great significance for the rational design of catalysts. However, how to quantify the structure-activity relationship of supported catalysts remains a great challenge. In this work, taking MoS2 and WS2 supported single atom catalysts (SACs) as prototypes, a simple descriptor, namely, effective d electron number (labeled as Φ), is constructed to quantitatively describe the effect of metal-support interaction on the nitrogen reduction reaction (NRR) activity. This descriptor merely consists of intrinsic properties of the catalyst (including the number of d electrons, electronegativity of the metal atoms and generalized electronegativity of the substrate atoms) and can accurately predict the limiting potential (UL) for the NRR, with no need for any density functional theory calculations. Moreover, this descriptor possesses superb expansibility that can be applied to other materials, including other metal dichalcogenide (MoSe2, MoTe2, WSe2, WTe2 and NbS2) and even MXene (V2CO2, Ti2CO2 and Nb2CO2)-supported SACs. On this basis, a fast screening of excellent NRR catalysts among these systems is performed and three promising NRR catalysts (i.e. Mo@WTe2, Mo@V2CO2 and Re@NbS2) are successfully selected with UL as low as -0.32, -0.24 and -0.31 V, respectively. This work offers new opportunities for advancing the rapid discovery of high-efficiency NRR catalysts, and the design principle is expected to be widely applicable to other catalytic systems and beyond.

Dynamic Stability of Copper Single-Atom Catalysts under Working Conditions.

The long-term stability of single-atom catalysts is a major factor affecting their large-scale commercial application. How to evaluate the dynamic stability of single-atom catalysts under working conditions is still lacking. Here, taking a single copper atom embedded in N-doped graphene as an example, the "constant-potential hybrid-solvation dynamic model" is used to evaluate the reversible transformation between copper single atoms and clusters under realistic reaction conditions. It is revealed that the adsorption of H is a vital driving force for the leaching of the Cu single atom from the catalyst surface. The more negative the electrode potential, the stronger the adsorption of H. As a result, the competitive hydrogen evolution reaction is inhibited, and Cu-N bonds are weakened, resulting in some Cu atoms being tethered on the catalyst surface and some being dissolved in the aqueous solution. The collision of the Cu atoms in the two states forms a transient Cu cluster structure as a true catalytic active site to promote CO2 reduction to ethanol. As the applied potential is released or switched to a positive value, hydroxyl radicals (OH•) play a dominant role in the oxidation process of the Cu cluster, and then Cu returns to the initial atomic dispersion state by redeposition, completing the reconstruction cycle of the copper catalyst. Our work provides a fundamental understanding of the dynamic stability of Cu single-atom catalysts under working conditions at the atomic level and calls for a reassessment of the stability of currently reported single-atom catalysts considering realistic reaction conditions.

A Universal Descriptor for Complicated Interfacial Effects on Electrochemical Reduction Reactions.

Supported catalysts have exhibited excellent performance in various reactions. However, the rational design of supported catalysts with high activity and certain selectivity remains a great challenge because of the complicated interfacial effects. Using recently emerged two-dimensional materials supported dual-atom catalysts (DACs@2D) as a prototype, we propose a simple and universal descriptor based on inherent atomic properties (electronegativity, electron type, and number), which can well evaluate the complicated interfacial effects on the electrochemical reduction reactions (i.e., CO2, O2, and N2 reduction reactions). Based on this descriptor, activity and selectivity trends in CO2 reduction reaction are successfully elucidated, in good agreement with available experimental data. Moreover, several potential catalysts with superior activity and selectivity for target products are predicted, such as CuCr/g-C3N4 for CH4 and CuSn/N-BN for HCOOH. More importantly, this descriptor can also be extended to evaluate the activity of DACs@2D for O2 and N2 reduction reactions, with very small errors between the prediction and reported experimental/computational results. This work provides feasible principles for the rational design of advanced electrocatalysts and the construction of universal descriptors based on inherent atomic properties.

Synthesis of Pd3 Sn and PdCuSn Nanorods with L12 Phase for Highly Efficient Electrocatalytic Ethanol Oxidation.

The crystal phase of nanomaterials is one of the key parameters determining their physicochemical properties and performance in various applications. However, it still remains a great challenge to synthesize nanomaterials with different crystal phases while maintaining the same composition, size, and morphology. Here, a facile, one-pot, wet-chemical method is reported to synthesize Pd3 Sn nanorods with comparable size and morphology but different crystal phases, that is, an ordered intermetallic and a disordered alloy with L12 and face-centered cubic (fcc) phases, respectively. The crystal phase of the as-synthesized Pd3 Sn nanorods is easily tuned by altering the types of tin precursors and solvents. Moreover, the approach can also be used to synthesize ternary PdCuSn nanorods with the L12 crystal phase. When used as electrocatalysts, the L12 Pd3 Sn nanorods exhibit superior electrocatalytic performance toward the ethanol oxidation reaction (EOR) compared to their fcc counterpart. Impressively, compared to the L12 Pd3 Sn nanorods, the ternary L12 PdCuSn nanorods exhibit more enhanced electrocatalytic performance toward the EOR, yielding a high mass current density up to 6.22 A mgPd -1 , which is superior to the commercial Pd/C catalyst and among the best reported Pd-based EOR electrocatalysts.

Preparation of Au@Pd Core-Shell Nanorods with fcc-2H-fcc Heterophase for Highly Efficient Electrocatalytic Alcohol Oxidation.

Controlled construction of bimetallic nanostructures with a well-defined heterophase is of great significance for developing highly efficient nanocatalysts and investigating the structure-dependent catalytic performance. Here, a wet-chemical synthesis method is used to prepare Au@Pd core-shell nanorods with a unique fcc-2H-fcc heterophase (fcc: face-centered cubic; 2H: hexagonal close-packed with a stacking sequence of "AB"). The obtained fcc-2H-fcc heterophase Au@Pd core-shell nanorods exhibit superior electrocatalytic ethanol oxidation performance with a mass activity as high as 6.82 A mgPd-1, which is 2.44, 6.96, and 6.43 times those of 2H-Pd nanoparticles, fcc-Pd nanoparticles, and commercial Pd/C, respectively. The operando infrared reflection absorption spectroscopy reveals a C2 pathway with fast reaction kinetics for the ethanol oxidation on the prepared heterophase Au@Pd nanorods. Our experimental results together with density functional theory calculations indicate that the enhanced performance of heterophase Au@Pd nanorods can be attributed to the unconventional 2H phase, the 2H/fcc phase boundary, and the lattice expansion of the Pd shell. Moreover, the heterophase Au@Pd nanorods can also serve as an efficient catalyst for the electrochemical oxidation of methanol, ethylene glycol, and glycerol. Our work in the area of phase engineering of nanomaterials (PENs) opens the way for developing high-performance electrocatalysts toward future practical applications.

Seeded Synthesis of Unconventional 2H-Phase Pd Alloy Nanomaterials for Highly Efficient Oxygen Reduction.

Crystal phase engineering of noble-metal-based alloy nanomaterials paves a new way to the rational synthesis of high-performance catalysts for various applications. However, the controlled preparation of noble-metal-based alloy nanomaterials with unconventional crystal phases still remains a great challenge due to their thermodynamically unstable nature. Herein, we develop a robust and general seeded method to synthesize PdCu alloy nanomaterials with unconventional hexagonal close-packed (hcp, 2H type) phase and also tunable Cu contents. Moreover, galvanic replacement of Cu by Pt can be further conducted to prepare unconventional trimetallic 2H-PdCuPt nanomaterials. Impressively, 2H-Pd67Cu33 nanoparticles possess a high mass activity of 0.87 A mg-1Pd at 0.9 V (vs reversible hydrogen electrode (RHE)) in electrochemical oxygen reduction reaction (ORR) under alkaline condition, which is 2.5 times that of the conventional face-centered cubic (fcc) Pd69Cu31 counterpart, revealing the important role of crystal phase on determining the ORR performance. After the incorporation of Pt, the obtained 2H-Pd71Cu22Pt7 catalyst shows a significantly enhanced mass activity of 1.92 A mg-1Pd+Pt at 0.9 V (vs RHE), which is 19.2 and 8.7 times those of commercial Pt/C and Pd/C, placing it among the best reported Pd-based ORR electrocatalysts under alkaline conditions.

Metastable 1T'-phase group VIB transition metal dichalcogenide crystals.

Metastable 1T'-phase transition metal dichalcogenides (1T'-TMDs) with semi-metallic natures have attracted increasing interest owing to their uniquely distorted structures and fascinating phase-dependent physicochemical properties. However, the synthesis of high-quality metastable 1T'-TMD crystals, especially for the group VIB TMDs, remains a challenge. Here, we report a general synthetic method for the large-scale preparation of metastable 1T'-phase group VIB TMDs, including WS2, WSe2, MoS2, MoSe2, WS2xSe2(1-x) and MoS2xSe2(1-x). We solve the crystal structures of 1T'-WS2, -WSe2, -MoS2 and -MoSe2 with single-crystal X-ray diffraction. The as-prepared 1T'-WS2 exhibits thickness-dependent intrinsic superconductivity, showing critical transition temperatures of 8.6 K for the thickness of 90.1 nm and 5.7 K for the single layer, which we attribute to the high intrinsic carrier concentration and the semi-metallic nature of 1T'-WS2. This synthesis method will allow a more systematic investigation of the intrinsic properties of metastable TMDs.

Photocatalytic conversion of CO to fuels with water by B-doped graphene/g-C3N4 heterostructure.

Photocatalytic reduction of carbon monoxide (CO) is a promising route to the production of high-value chemicals and fuels, as a supplement to high energy-input Fischer-Tropsch synthesis (FTS) and a key step in direct photo/electro-reduction CO2 to multi-carbon products. However, many current research efforts for high-efficiency FTS/CO2 reduction mainly focus on the metal-based catalysts, while metal-free and solar-driven photocatalysts are rarely explored. Here, by means of Lewis acid sites, a metal-free composite photocatalyst for CO reduction, namely boron (B) doped-graphene/g-C3N4 heterostructure, is proposed. First-principles calculations show that the dopants (B) as catalytic sites can effectively capture and activate CO molecules and reduce CO to CH3OH and CH4 in different doping content. It is worth noting that C2 products, i.e., C2H5OH, can be produced with low free energy barriers on para-doped graphene/g-C3N4. Meanwhile, the competitive hydrogen evolution reaction (HER) can be greatly suppressed, leading to the high selectivity of CO reduction. Moreover, the formation of a built-in electric field in heterostructure enhances the separation of photogenerated electrons and holes, which further accelerates the transmission of photogenerated electrons to the catalytic sites and improves the reaction efficiency. Overall, this work not only proposes a new strategy from a new perspective to solve problems of high energy consumption and low selectivity of FTS, but also provides a tandem strategy to solve problems of CO2 to multi-carbon products.