Deep Hydrogenation Research Articles

Switching between C2+ Products and CH4 in CO2 Electrolysis by Tuning the Composition and Structure of Rare-Earth/Copper Catalysts.

Rational regulation of the reaction pathway to produce the desired products is one of the most significant challenges in the electrochemical CO2 reduction reaction (CO2RR). Herein, we designed a series of rare-earth Cu catalysts with mixed phases. It was found that the products could be switched from C2+ to CH4 by tuning the composition and structure of the catalysts. Particularly at the Cu/Sm atomic ratio of 9/1 (Cu9Sm1-Ox), the Faradaic efficiency (FE) for C2+ products (FEC2+) could reach 81% at 700 mA cm-2 with negligible CH4. However, the FE of CH4 (FECH4) was 65% at 500 mA cm-2 over Cu1Sm9-Ox (Cu/Sm = 1/9), and the FEC2+ was extremely low. Experiments and theoretical studies indicated that the stable CuSm2O4 phase existed in all the catalysts within the Cu/Sm range of 9/1 to 1/9. At a high Cu content, the catalyst was composed of CuSm2O4 and Cu phases. The small amount of Sm could enhance the binding strength of *CO and facilitate C-C coupling. Conversely, at a high Sm content, the catalyst was composed of CuSm2O4 and Sm2O3 phases. Sm could effectively stabilize bivalent Cu and enrich proton donors, lowering the reaction energy of *CO for deep hydrogenation to generate CH4. In both pathways, the stable CuSm2O4 phase could cooperate with the Cu or Sm2O3 phases, which induced the formation of different microenvironments to generate different products. This strategy also had commonality with other Cu-rare-earth (La, Pr, and Eu) catalysts to boost the CO2RR for C2+ or CH4 production.

A comparative study of the reaction mechanism for deep reduction hydrogen production using two special steel solid wastes and a chemical looping hydrogen production scheme

Pickling sludge (PS) and presintered waste (PW) are two special steel solid wastes that have potential as oxygen carriers due to their Fe content. Using these raw materials to produce hydrogen allows for the resource utilization of solid waste, which has good environmental effects. Here, we studied the deep reduction-hydrogen production characteristics. Specifically, the effects of temperature, papermaking sludge (PMS) blended ratio, and reaction time on the deep reduction characteristics of Fe in pickling sludge and presintered waste were studied. On this basis, the study also aimed to investigate the effects of temperature and PMS blended ratio on hydrogen production. The results indicated that when exposed to high temperature, PMS shows the ability to effectively reduce pickling sludge and presintered waste. The maximum Fe recovery rate can reach 65.63 and 96.94 % in a fixed bed reactor operating at 700 °C and a blended ratio of approximately 10 %. Under the conditions of 900 °C and 15 %/50 % papermaking sludge addition, the Fe content within pickling sludge and presintered waste was reduced to FeCr2O4 and FeO, respectively. Subsequently, during the reaction with steam, Fe2O3 and Fe3O4 were generated in PS and PW, respectively. The hydrogen production per unit mass of Fe2O3 in pickling sludge is higher due to the existence of the FeCr2O4 spinel structure in the reduction product of pickling sludge. According to the above results, two hydrogen production strategies of PS and PW through different deep reduction paths are proposed.

Effect of solvent viscosity on the activation barrier of hydrogen tunneling in the lipoxygenase reaction

Hydrogen tunneling in enzyme reactions has played an important role in linking protein thermal motions to the chemical steps of catalysis. Lipoxygenases (LOXs) have served as model systems for such reactions, showcasing deep hydrogen tunneling mechanisms associated with enzymatic C–H bond cleavage from polyunsaturated fatty acids. Here, we examined the effect of solvent viscosity on the protein thermal motions associated with LOX catalysis using trehalose and glucose as viscogens. Kinetic analysis of the reaction of the paradigm plant orthologue, soybean lipoxygenase (SLO), with linoleic acid revealed no effect on the first-order rate constants, kcat, or activation energy, Ea. Further studies of SLO active site mutants displaying varying Eas, which have been used to probe catalytically relevant motions, likewise provided no evidence for viscogen-dependent motions. Kinetic analyses were extended to a representative fungal LOX from M. oryzae, MoLOX, and a human LOX, 15-LOX-2. While MoLOX behaved similarly to SLO, we show that viscogens inhibit 15-LOX-2 activity. The latter implicates viscogen sensitive, conformational motions in animal LOX reactions. The data provide insight into the role of water hydration layers in facilitating hydrogen (quantum) tunneling in LOX.

Xylene Synthesis Through Tandem CO2 Hydrogenation and Toluene Methylation Over a Composite ZnZrO Zeolite Catalyst.

Selective synthesis of specific value-added aromatics from CO2 hydrogenation is of paramount interest for mitigating energy and climate problems caused by CO2 emission. Herein, we report a highly active composite catalyst of ZnZrO and HZSM-5 (ZZO/Z5-SG) for xylene synthesis from CO2 hydrogenation via a coupling reaction in the presence of toluene, achieving a xylene selectivity of 86.5 % with CO2 conversion of 10.5 %. A remarkably high space time yield of xylene could reach 215 mg gcat -1 h-1 , surpassing most reported catalysts for CO2 hydrogenation. The enhanced performance of ZZO/Z5-SG could be due to high dispersion and abundant oxygen vacancies of the ZZO component for CO2 adsorption, more feasible hydrogen activation and transfer due to the close interaction between the two components, and enhanced stability of the formate intermediate. The consumption of methoxy and methanol from the deep hydrogenation of formate by introduced toluene also propels an oriented conversion of CO2 .

Xylene Synthesis Through Tandem CO2 Hydrogenation and Toluene Methylation Over a Composite ZnZrO Zeolite Catalyst

AbstractSelective synthesis of specific value‐added aromatics from CO2 hydrogenation is of paramount interest for mitigating energy and climate problems caused by CO2 emission. Herein, we report a highly active composite catalyst of ZnZrO and HZSM‐5 (ZZO/Z5‐SG) for xylene synthesis from CO2 hydrogenation via a coupling reaction in the presence of toluene, achieving a xylene selectivity of 86.5 % with CO2 conversion of 10.5 %. A remarkably high space time yield of xylene could reach 215 mg gcat−1 h−1, surpassing most reported catalysts for CO2 hydrogenation. The enhanced performance of ZZO/Z5‐SG could be due to high dispersion and abundant oxygen vacancies of the ZZO component for CO2 adsorption, more feasible hydrogen activation and transfer due to the close interaction between the two components, and enhanced stability of the formate intermediate. The consumption of methoxy and methanol from the deep hydrogenation of formate by introduced toluene also propels an oriented conversion of CO2.

Tuning hydrogenation chemistry of Pd-based heterogeneous catalysts by introducing homogeneous-like ligands

Noble metals have been extensively employed in a variety of hydrotreating catalyst systems for their featured functionality of hydrogen activation but may also bring side reactions such as undesired deep hydrogenation. It is crucial to develop a viable approach to selectively inhibit side reactions while preserving beneficial functionalities. Herein, we present modifying Pd with alkenyl-type ligands that forms homogeneous-like Pd-alkene metallacycle structure on the heterogeneous Pd catalyst to achieve the selective hydrogenolysis and hydrogenation. Particularly, a doped alkenyl-type carbon ligand on Pd-Fe catalyst is demonstrated to donate electrons to Pd, creating an electron-rich environment that elongates the distance and weakens the electronic interaction between Pd and unsaturated C of the reactants/products to control the hydrogenation chemistry. Moreover, high H2 activation capability is maintained over Pd and the activated H is transferred to Fe to facilitate C-O bond cleavage or directly participate in the reaction on Pd. The modified Pd-Fe catalyst displays comparable C-O bond cleavage rate but much higher selectivity (>90%) than the bare Pd-Fe (<50%) in hydrotreating of diphenyl ether (DPE, modelling the strongest C-O linkage in lignin) and enhanced ethene selectivity (>90%) in acetylene hydrogenation. This work sheds light on the controlled synthesis of selective hydrotreating catalysts via mimicking homogeneous analogues.

Study on the preparations of Mo and W powders via carbothermal pre-reduction process of MoO3 or WO3

In this paper, ultrafine Mo (W) powders were obtained by a two-stage reduction process consisting of carbothermal pre-reduction of MoO3 (WO3) and deep hydrogen reduction. The increase of reaction time was conducive to reduce the residual carbon contents of carbothermally pre-reduced products without significantly affecting the particle sizes. The particle sizes of carbothermic reduction products of MoO3 and WO3 were 186–192 nm and 141–146 nm as increasing holding time from 1 h to 4 h, respectively, while the residual carbon contents decreased from 0.036 wt% to 0.025 wt%, as well as from 0.045 wt% to 0.032 wt%, respectively. In addition, with the decrease in particle size of carbon black from 200 to 300 nm to 50 nm, the particle sizes of carbothermic reduction products of MoO3 and WO3 were gradually decreased from 322 nm to 188 nm and from 261 nm to 146 nm, respectively, while their residual carbon contents were 0.025–0.028 wt%, as well as 0.028–0.031 wt%, respectively. After the deep hydrogen reduction of carbothermal reduction products, the residual carbon contents of finally obtained ultrafine Mo and W powders were further reduced.

Effects of CeO2, TiO2, and TiO2-CeO2 Supports on Catalytic Performance of Ni2P in Hydrodeoxygenation of Anisole

This work examined the effects of supports for nickel phosphide (Ni2P) catalysts on anisole hydrodeoxygenation (HDO) using synthesized CeO2, TiO2, and TiO2-CeO2 supports and commercial supports (denoted as CeO2-L and TiO2-L) along with bulk Ni2P. Characterization revealed that Ni2P nanoparticles were well dispersed on the synthesized CeO2. Ni2P/CeO2 exhibited the highest activity on a catalyst weight basis among those Ni2P on synthesized supports as well as the common materials such as SiO2, Al2O3, and activated carbon. Ni2P/TiO2-CeO2 (at a Ti/Ce molar ratio of 0.98) afforded superior reactivity to Ni2P/CeO2 based on turnover frequency (TOF, h–1), which points to more active sites on Ni2P/TiO2-CeO2 than on Ni2P/CeO2. The TOF of anisole on catalysts decreased in the following order: Ni2P/Ti0.98Ce0.02O2 > Ni2P/TiO2 > Ni2P/CeO2 > bulk Ni2P. The type of supports employed for Ni2P also influenced the product distributions and thus HDO pathways. Ni2P/CeO2 favored benzene selectivity, and this may be related to the relative electron enrichment on the Niδ+ site of Ni2P/CeO2 that facilitated benzene desorption from the catalyst surface after demethoxylation of anisole. Ni2P/TiO2-CeO2 exhibited significantly higher cyclohexane selectivity, which may be attributed to the lower electron density on Niδ+ of Ni2P/TiO2-CeO2 and the acidity of binary support, promoting the deep hydrogenation of benzene to cyclohexane. The presence of phenol when Ni2P/TiO2 and Ni2P/TiO2-CeO2 were employed in anisole HDO could be correlated with the acidity of TiO2, which led to methylation of anisole. Adding a small amount of CeO2 in TiO2 and using it as support synergistically improved the TOF and suppressed phenol formation while increasing cyclohexane selectivity. Both Ni2P/CeO2 and Ni2P/TiO2-CeO2 are promising catalysts in anisole HDO for the tunable target products of benzene and cyclohexane, respectively.

Effects of the cementite morphology on the hydrogen trapping behavior in the pipeline steel

PurposeThe purpose of this study is to investigate the effects of the cementite morphology on the hydrogen trapping behavior in low-alloy pipeline steel.Design/methodology/approachIn this study, the hydrogen trapping behavior in low-alloy pipeline steel was quantitatively studied by a combination of microstructural observations, electrochemical hydrogen permeation experiments and thermal desorption spectroscopy (TDS) analyses.FindingsP-1 and P-2 steels are two samples with different microstructures. The morphology of cementite precipitates in the P-1 and P-2 steels was different. Lamellar cementite is present in P-2 steel and only granular cementite in P-1 steel, which led to a better irreversible hydrogen trapping ability of P-2 steel, which was confirmed by subsequent hydrogen permeation and TDS experiments.Originality/valueThe study of these deep hydrogen trap sites is helpful in improving the hydrogen embrittlement resistance of low-alloy pipeline steels.

Real-time hydrogen release and dispersion modelling of hydrogen refuelling station by using deep learning probability approach

Hydrogen release and dispersion from hydrogen refuelling stations have the potential to cause explosion disaster and bring significant causalities and economic losses to the surroundings. Real-time spatial hydrogen plume concentration prediction is essential for the quick emergency response planning to dissipate such flammable vapor cloud and prevent explosion disaster. Deep learning approaches have recently been applied to real-time gas release and dispersion modeling, however, are ‘over-confident’ for spatial plume concentration and boundary estimation, which could not support the robust decision-makings. This study proposes a hybrid deep probability learning-based spatial hydrogen plume concentration prediction model, namely DPL_H2Plume by integrating deep learning and Variational Bayesian Inference. Numerical model of hydrogen release and dispersion from hydrogen refuelling station is built to construct the benchmark dataset. By using such dataset, two pre-defined parameters, namely Monte Carlo sampling number m = 300 and dropout probability p = 0.1 are determined to ensure the model's tradeoff between inference accuracy and efficiency. Comparison between our proposed model and the state-of-the-art model is also conducted. The results demonstrate that our model exhibits a competitive accuracy of R2 = 0.97 as well as an inference time 3.32 s. In addition, our model gives the comprehensive estimations including not only spatial hydrogen plume concentration but also its uncertainty. Also, our model provides the more accurate estimation at plume boundary compared to the state-of-the-art model. Overall, our proposed model could provide reliable alternative for constructing a digital twin for emergency management of hydrogen refuelling station.

Fabrication of highly oxidized Pt single-atom catalysts to suppress the deep hydrogenation of unsaturated aldehydes

In this work, we first reported the fabrication of single-atom Pt catalysts with high oxidation state through a mild hydrolysis method using platinum acetylacetonate as the precursor and SBA-15 coated with functional FeOx nanoclusters as support, and evaluate their catalytic performance towards unsaturated aldehydes hydrogenation. Pt1-FeOx/SBA-15 featuring the high coordination number of Pt-O exhibited markedly high selectivity for hydrogenation of CO group (> 95 %) when cinnamaldehyde conversion is 100 %, and further hydrogenation of target product could be efficiently inhibited over a prolonged period of time, and the universality of chemoselectivity was also evidenced in other unsaturated aldehydes. The experimental results and theoretical calculations revealed that the synergism of highly electron-deficient Pt single-atoms and FeOx species is responsible for the selectivity control and the inhibition of further hydrogenation. The developed strategy offers a facile approach to the rational design of high-efficient single-atom catalysts for the selective hydrogenation with multiple intermediates.

Design and preparation of Pt@SSZ-13@β core-shell catalyst for hydrocracking of naphthalene

A Pt@SSZ-13@β core-shell catalyst is designed and successfully prepared for investigating the effects of spillover hydrogenation on hydrocracking of naphthalene. The Pt NPs encapsulated in SSZ-13 cages are inaccessible to naphthalene due to its lager size than the pore size of SSZ-13. Thus, hydrogenation functional over Pt@SSZ-13@β is mainly realized via spillover hydrogenation. Pt@SSZ-13@β exhibits higher selectivity to the desired BTX and less naphthenic products than (Pt/SSZ-13)@β and Pt/(SSZ-13@β) at above 90 % naphthalene conversion. These results indicate the hydrogenation modes resulting from the location of the supported Pt NPs in core-structure catalysts can affect the metal-acid balance, and the spillover hydrogenation can effectively suppress the deep hydrogenation of tetralin in hydrocracking of naphthalene, thereby changing the reaction path and improving the selectivity of BTX. In addition, Pt@SSZ-13@β shows a better sulfur-tolerant ability than Pt/(SSZ-13@β). This work provides a new synthetic strategy for preparing zeolite-based bifunctional catalyst.

Native aluminum as indicator of hydrogen degassing in the formation of hydrocarbon fields

This work considers the possibility of native aluminum transport with hydrogen fluid, its deposition and preservation in sedimentary rocks, as well as an assessment of the conditions under which this is possible. This problem is currently debatable and is considered in a number of publications. Native aluminum was found in different types of sedimentary rocks of oil-and-gas-bearing basins. So the presence of native aluminum spherulas was established in the dolomites of the Dnipro-Donetsk Basin. By the example of these findings this work shows that the necessary conditions for the formation and long-term preservation of native aluminum are: its migration with the hydrogen flow into the upper layers of the Earth’s crust, the creation of temperature and pressure conditions causing water to vaporize, and the formation of a protective film on the surface of the formed native aluminum. The process of native aluminum formation in the sedimentary rocks of oil-and-gas-bearing deposits of the Dnipro-Donetsk Rift described in this work, as well as its findings in other basins indicates the typical character of this process for rift structures of hydrocarbon accumulation. It was assumed, that the oil-and-gas-bearing structure of Dnipro-Donetsk Rift is mantle origin and represents a giant source of deep hydrogen. Some of this hydrogen is consumed to form hydrocarbon accumulations, including known oil and gas deposits, and some of it degasses into the uppermost layers of the Earth’s crust. Independent hydrogen fields can also form there, as was the case during the formation of the deposit of geological hydrogen in Mali. It was shown, that the presence of hydrocarbons in the fluids does not affect the processes associated with aluminum. The results obtained indicate significant flows of hydrogen from the mantle to the upper horizons of the Earth’s crust. Thus, native aluminum, as well as other native oxyphilic metals in sedimentary rocks of oil-and-gas bearing basins is a search marker of both hydrocarbon accumulations and the important role of deep geological hydrogen in the formation of these accumulations and its possible accumulation in the most reliable traps.

Electrocatalytic deep hydrogenation of 4-chlorophenol into cyclohexanol on microchannel-enhanced Ru/TiO2 for wastewater detoxification and simultaneous resource recovery

Chlorophenols (CPs) are among the most significant environmental concerns worldwide, which pose a serious threat to global water safety and human health. Herein, a novel electrocatalytic hydrogenation (ECH) pathway was proposed for the detoxification of CPs, where both the cleavage of C−Cl bond and hydrogenation of phenol ring take place. Employing a fibrous Ru/TiO2 electrode (f-Ru/TiO2) with massive microchannels, we achieved over 99.8% removal of 1 mM 4-chlorophenol (4-CP) within 60 min, with a corresponding kinetic constant of 0.101 min−1. The toxic 4-CP was completely transformed into cyclohexanol, which possesses almost no biotoxicity and could be rapidly recovered from treated water. The ECH system exhibited high 4-CP removal efficiencies at different pH conditions (3−11). Besides, a 4-CP removal efficiency of over 99.1% was achieved even at a remarkably high concentration (10 mM). Mechanism analysis confirms that direct electron transfer dominates the ECH process, while the contribution of atomic hydrogen (H*) is less prominent. Overall, this study demonstrates an inspiring ECH approach with enhanced pollutants diffusion and electron transfer for not only the detoxification of but also resource recovery from chlorophenol wastewater.

Enhanced Alkene Selectivity for Transfer Semihydrogenation of Alkynes over Electron-Deficient Pt Nanoparticles Encapsulated in Hollow Silica Nanospheres.

In this work, we report that Pt nanoparticles confined in hollow porous silica nanospheres (Pt@HPSNs) function as highly selective catalysts for the transfer hydrogenation of phenylacetylene to styrene with ammonia borane. Relative to the deep hydrogenation of phenylacetylene to ethylbenzene over the supported Pt/SiO2, Pt@HPSNs exhibit above 88% of styrene selectivity at nearly 100% of phenylacetylene conversions, and the high selectivity of Pt@HPSNs can be maintained even at high ammonia borane/phenylacetylene ratios and longer reaction time. The Pt 4f X-ray photoelectron spectrum of Pt@HPSNs shows a remarkable ∼1.5 eV shift to high binding energy, proving the nature of electron deficiency of such encapsulated Pt nanoparticles. Combined with extremely minor transfer hydrogenation of styrene to ethylbenzene when styrene as substrates, the enhanced styrene selectivity of Pt@HPSNs is ascribed to the electron deficiency of encapsulated Pt nanoparticles, which leads to the fast desorption of styrene and thus avoids deep hydrogenation.

Heterogeneous Hydrogenation with Hydrogen Spillover Enabled by Nitrogen Vacancies on Boron Nitride-Supported Pd Nanoparticles.

Heterogeneous hydrogenation with hydrogen spillover has been demonstrated as an effective route to achieve high selectivity towards target products. More effort should be paid to understand the complicated correlation between the nature of supports and hydrogenation involving hydrogen spillover. Herein, we report the development of the hydrogenation system of hexagonal boron nitride (h-BN)-supported Pd nanoparticles for the hydrogenation of aldehyde/ketones to alcohols with hydrogen spillover. Nitrogen vacancies in h-BN determine the feasibility of hydrogen spillover from Pd to h-BN. The hydrogenation of aldehyde/ketones with hydrogen spillover from Pd proceeds on nitrogen vacancies on h-BN. The weak adsorption of alcohols to h-BN inhibits the deep hydrogenation of aldehyde/ketones, thus leading to high catalytic selectivity to alcohols. Moreover, the hydrogen spillover-based hydrogenation mechanism makes the catalyst system exhibit a high tolerance to CO poisoning.

Heterogeneous Hydrogenation with Hydrogen Spillover Enabled by Nitrogen Vacancies on Boron Nitride‐Supported Pd Nanoparticles

AbstractHeterogeneous hydrogenation with hydrogen spillover has been demonstrated as an effective route to achieve high selectivity towards target products. More effort should be paid to understand the complicated correlation between the nature of supports and hydrogenation involving hydrogen spillover. Herein, we report the development of the hydrogenation system of hexagonal boron nitride (h‐BN)‐supported Pd nanoparticles for the hydrogenation of aldehydes/ketones to alcohols with hydrogen spillover. Nitrogen vacancies in h‐BN determine the feasibility of hydrogen spillover from Pd to h‐BN. The hydrogenation of aldehydes/ketones with hydrogen spillover from Pd proceeds on nitrogen vacancies on h‐BN. The weak adsorption of alcohols to h‐BN inhibits the deep hydrogenation of aldehydes/ketones, thus leading to high catalytic selectivity to alcohols. Moreover, the hydrogen spillover‐based hydrogenation mechanism makes the catalyst system exhibit a high tolerance to CO poisoning.

Tuning the CO2 Hydrogenation Selectivity of Rhodium Single‐Atom Catalysts on Zirconium Dioxide with Alkali Ions

AbstractTuning the coordination environments of metal single atoms (M1) in single‐atom catalysts has shown large impacts on catalytic activity and stability but often barely on selectivity in thermocatalysis. Here, we report that simultaneously regulating both Rh1 atoms and ZrO2 support with alkali ions (e.g., Na) enables efficient switching of the reaction products from nearly 100 % CH4 to above 99 % CO in CO2 hydrogenation in a wide temperature range (240–440 °C) along with a record high activity of 9.4 molCO gRh−1 h−1 at 300 °C and long‐term stability. In situ spectroscopic characterization and theoretical calculations unveil that alkali ions on ZrO2 change the surface intermediate from formate to carboxy species during CO2 activation, thus leading to exclusive CO formation. Meanwhile, alkali ions also reinforce the electronic Rh1‐support interactions, endowing the Rh1 atoms more electron deficient, which improves the stability against sintering and inhibits deep hydrogenation of CO to CH4.

Tuning the CO2 Hydrogenation Selectivity of Rhodium Single-Atom Catalysts on Zirconium Dioxide with Alkali Ions.

Tuning the coordination environments of metal single atoms (M1 ) in single-atom catalysts has shown large impacts on catalytic activity and stability but often barely on selectivity in thermocatalysis. Here, we report that simultaneously regulating both Rh1 atoms and ZrO2 support with alkali ions (e.g., Na) enables efficient switching of the reaction products from nearly 100 % CH4 to above 99 % CO in CO2 hydrogenation in a wide temperature range (240-440 °C) along with a record high activity of 9.4 molCO gRh -1 h-1 at 300 °C and long-term stability. In situ spectroscopic characterization and theoretical calculations unveil that alkali ions on ZrO2 change the surface intermediate from formate to carboxy species during CO2 activation, thus leading to exclusive CO formation. Meanwhile, alkali ions also reinforce the electronic Rh1 -support interactions, endowing the Rh1 atoms more electron deficient, which improves the stability against sintering and inhibits deep hydrogenation of CO to CH4 .

On-Demand, Highly Tunable, and Selective 5-Hydroxymethylfurfural Hydrogenation to Furan Diols Enabled by Ni and Ni3Ga Alloy Catalysts

Catalytic conversion of the biobased platform chemical 5-hydroxymethylfurfural (HMF) into high-value-added products (e.g., diols) has attracted considerable attention, where controlling the products’ selectivity is a crucial and challenging issue. Herein, a series of hydrotalcite-based Ni and Ni3Ga alloy catalysts were prepared for HMF hydrogenation into furan diols. By optimizing the loaded metal and reduction temperature, >99% BHMTHF and 95.6% BHMF yields were gained over Ni1.5Al-LDO-700 and Ni1.5GaAl-LDO-700, respectively, under mild conditions. Characterizations and DFT calculations showed that the doped Ga resulted in charge transfer from Ga to Ni and disrupted the Ni arrangement, which weakened the furan ring adsorption and favored its tilted adsorption on the Ni3Ga alloy, consequently inhibited deep hydrogenation, and selectively produced BHMF. These catalysts were also versatile for hydrogenation of other furan aldehydes, achieving high selectivity toward un-/saturated alcohols on demand. This study provides an advanced strategy for the rational design of superior catalysts for tuning product selectivity on demand, with practical potential for upgrading biomass-derived platform molecules.